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PubMed2003

Singlet oxygen-mediated damage to proteins and its consequences.

Proteins comprise approximately 68% of the dry weight of cells and tissues and are therefore potentially major targets for oxidative damage. Two major types of processes can occur during the exposure of proteins to UV or visible light. The first of these involves direct photo-oxidation arising from the absorption of UV radiation by the protein, or bound chromophore groups, thereby generating excited states (singlet or triplets) or radicals via photo-ionisation. The second major process involves indirect oxidation of the protein via the formation and subsequent reactions of singlet oxygen generated by the transfer of energy to ground state (triplet) molecular oxygen by either protein-bound, or other, chromophores. Singlet oxygen can also be generated by a range of other enzymatic and non-enzymatic reactions including processes mediated by heme proteins, lipoxygenases, and activated leukocytes, as well as radical termination reactions. This paper reviews the data available on singlet oxygen-mediated protein oxidation and concentrates primarily on the mechanisms by which this excited state species brings about changes to both the side-chains and backbone of amino acids, peptides, and proteins. Recent work on the identification of reactive peroxide intermediates formed on Tyr, His, and Trp residues is discussed. These peroxides may be important propagating species in protein oxidation as they can initiate further oxidation via both radical and non-radical reactions. Such processes can result in the transmittal of damage to other biological targets, and may play a significant role in bystander damage, or dark reactions, in systems where proteins are subjected to oxidation.

Humans↗
PubMed1997

Singlet oxygen mediates the activation of JNK by UVA radiation in human skin fibroblasts.

Ultraviolet A (UVA: 320-400 nm) radiation activates c-Jun-N-terminal kinase (JNK 2) in human skin fibroblasts. Exposure of cells to UVA (300 kJ/m2) led to a 5-fold induction of JNK-activity which was significantly increased in the presence of D2O, an enhancer of the lifetime of singlet oxygen. Sodium azide, a quencher of singlet oxygen, abolished the activation of JNK. A hydroxyl radical scavenger, mannitol, had no effect. Furthermore, photochemically produced singlet oxygen (Rose Bengal plus white light) was found to induce JNK activity. This was enhanced by D2O and inhibited by azide. Thus, singlet oxygen activates and mediates the UVA-induced activation of JNK.

Calcium-Calmodulin-Dependent Protein Kinases↗
PubMed2002

Kinetics and efficiency of excitation energy transfer from chlorophylls, their heavy metal-substituted derivatives, and pheophytins to singlet oxygen.

Time-resolved measurements of the singlet oxygen infrared (1269 nm) luminescence were used to follow the kinetics and efficiency of excitation energy transfer (EET) between chlorophyll (Chl) derivatives and oxygen in acetone. The studied pigments were Mg-Chl a and b and their heavy metal (Cu(2+) and Zn(2+))-substituted analogues, as well as pheophytin (Pheo) a and b. The efficiency of EET from chlorophyll to oxygen was highly dependent on the central ion in the pigment. Cu-Chl a and Cu-Chl b had the lowest efficiencies of singlet oxygen production, while Pheo a had a higher one, and Zn-Chl a had a similar one compared to Mg-Chl a. Also the side chain (position C-7, i.e. Chl a vs. Chl b) influenced the efficiency of singlet oxygen formation. In the case of square-planar complexes like Cu-Chl and Pheo, EET was more efficient in the Chl a derivatives than in those of Chl b; the opposite effect was observed in the case of the five- or six-coordinated Mg-Chl and Zn-Chl. As for the lifetime of the Chl triplet state, the most striking difference to Mg-Chl again was found in the case of Cu-Chls, which had much shorter lifetimes. Furthermore, the central ion in Chl affected the physical quenching of singlet oxygen: its efficiency was decreasing from Mg-Chl through Zn-Chl over Cu-Chl to Pheo. The results are discussed in the context of the oxidative stress accompanying heavy metal-induced stress in plants.

Chlorophyll↗
PubMed1999

New sensitive agents for detecting singlet oxygen by electron spin resonance spectroscopy.

Free radicals are well-established transient intermediates in chemical and biological processes. Singlet oxygen, though not a free radical, is also a fairly common reactive chemical species. It is rare that singlet oxygen is studied with the electron spin resonance (ESR) technique in biological systems, because there are few suitable detecting agents. We have recently researched some semiquinone radicals. Specifically, our focus has been on bipyrazole derivatives, which slowly convert to semiquinone radicals in DMSO solution in the presence of potassium tert-butoxide and oxygen. These bipyrazole derivatives are dimers of 3-methyl-1-phenyl-2-pyrazolin-5-one and have anti-ischemic activities and free radical scavenging properties. In this work, we synthesized a new bipyrazole derivative, 4,4'-bis(1p-carboxyphenyl-3-methyl-5-hydroxyl)-pyrazole, DRD156. The resulting semiquinone radical, formed by reaction with singlet oxygen, was characterized by ESR spectroscopy. DRD156 gave no ESR signals from hydroxyl radical, superoxide, and hydrogen peroxide. DRD156, though, gives an ESR response with hypochlorite. This agent, nevertheless, has a much higher ability to detect singlet oxygen than traditional agents with the ESR technique.

Dimethyl Sulfoxide↗
PubMed2000

Quenching of singlet oxygen (1deltag) by cobalt complexes with four nitrogen atoms in the equatorial plane.

The quenching of singlet oxygen (1deltag) by cobalt(III)-bis-1,2-benzosemiquinone-diiminato complexes (general structure LCo(111)(BQDI)2ClO4) has been studied in different solvents by measuring the singlet oxygen phosphorescence decay in time-resolved experiments. The axial ligand (Ph3As, Ph3Sb, N-methyl-imidazole, pyrrolidine) has practically no influence on the quenching; however, the chlorinated benzosemiquinone-diiminato complex has a markedly lower quenching rate constant. The solvent effects can be fully explained by the difference in viscosity, which supports the assumption that the quenching is diffusion controlled. The reactive radius of the encounter pair has been estimated to be 0.3 nm, shorter than the radius of the complex itself, which points to the fact that singlet oxygen must approach the central cobalt atom at the (partially) open axial position. The significance of these results regarding the quenching of singlet oxygen by vitamin B12 derivatives is discussed.

Cobalt↗
PubMed2006

Christopher Foote's discovery of the role of singlet oxygen [1O2 (1Delta g)] in photosensitized oxidation reactions.

The chemistry of singlet molecular oxygen [1O2 (1Delta g)], its importance in atmospheric, biological, and therapeutic processes, and its use as a reagent in organic synthesis have been of considerable interest. Many aspects of singlet oxygen chemistry have emanated from the work of Christopher S. Foote and co-workers. Singlet oxygen is a historically interesting molecule with an unusual story connected with its discovery. Foote and Wexler conducted experiments in the 1960s where evidence was obtained supporting 1O2 generation via two independent routes: (1) a photochemical reaction (dye-sensitized photooxidation) and (2) a chemical reaction (NaOCl with H2O2). An important factor in the discovery of 1O2 as the critical reaction intermediate in dye-sensitized photooxygenations was Foote's reassessment of the chemical literature of the 1930s, when 1O2 was suggested to be a viable intermediate in dye-sensitized photooxidation reactions. Experiments that used silica gel beads provided evidence for a volatile diffusible oxidant such as 1O2. However, a contemporaneous quarrel surrounded this early work, and the possible existence of solution-phase 1O2 was ignored for over 2 decades. Not long after Foote's initial studies were published in 1964, the idea of singlet oxygen as an intermediate in photooxidation chemistry gained increasing recognition and verification in organic, gas phase, and biological processes. There are many documented impacts that 1O2 has had and continues to have on biology and medicine, for example, photodynamic therapy and plant defenses.

History, 20th Century↗
PubMed2002

Bis-cyclometalated Ir(III) complexes as efficient singlet oxygen sensitizers.

We report the singlet oxygen sensitization properties of a series of bis-cyclometalated Ir(III) complexes (i.e., (bt)2Ir(acac), (bsn)2Ir(acac), and (pq)2Ir(acac); bt = 2-phenylbenzothiazole, bsn = 2-(1-naphthyl)benzothiazole, pq = 2-phenylquinoline, and acac = acetylacetonate). Complexes with acetylacetonate ancillary ligands give singlet oxygen quantum yields near unity (PhiDelta = (0.7-1.0) +/- 0.1), whether exciting the ligand-based state or the lowest energy excited state (MLCT + 3LC). The singlet oxygen quenching rates for these beta-diketonate complexes were found to be small [(5 +/- 2) x 105 to (6 +/- 0.2) x 106 M-1 s-1], roughly 3 orders of magnitude slower than the corresponding phosphorescence quenching rate. Similar complexes were prepared with glycine or pyridine tethered to the Ir(III) center (i.e., (bsn)2Ir(gly) and (bt)2Ir(py)Cl; gly = glycine and py = pyridine). The glycine and pyridine derivatives give high singlet oxygen yields (PhiDelta = (0.7-1.0) +/- 0.1).

Iridium↗
PubMed2006

DNA-programmed control of photosensitized singlet oxygen production.

DNA sequence-controlled on-and-off switching of a singlet oxygen sensitizer has been developed and demonstrated. The singlet oxygen photosensitizer pyropheophorbide-a (P) was attached to a 15-mer nucleotide sequence. A molecule that could quench the sensitizer, the so-called "black hole quencher 3" (Q), was attached to a complementary nucleotide strand. Upon hybridization of the two conjugates, singlet oxygen production from P was completely shut down. Upon the addition of a third DNA sequence that can displace and release the P-DNA conjugate from the P-Q pair, up to 85% of the singlet oxygen production was recovered. This system is a model for a benign drug that becomes active only in the presence of a specific targeted nucleotide sequence.

Chlorophyll↗
PubMed2006

Preparative singlet oxygenation of linoleate provides doubly allylic dihydroperoxides: putative intermediates in the generation of biologically active aldehydes in vivo.

Photoinduced oxygenation generates biologically active, oxidatively truncated lipids in the retina. Previously, doubly allylic dihydroperoxides, 9,12-dihydroperoxyoctadeca-10,13-dienoic acid (9,12-diHPODE) and 10,13-dihydroperoxyoctadeca-8,11-dienoic acid (10,13-diHPODE), were postulated as key intermediates in the free radical-promoted oxidative fragmentation of linoleate that generates aldehydes, such as the cytotoxic gamma-hydroxyalkenal 4-hydroxy-2-nonenal (HNE), in vivo. We now report an efficient preparation of regioisomerically pure 9,12- and 10,13-diHPODE, devised to enable studies of their fragmentation reactions. Free radical-induced oxygenation of linoleate initially generates conjugated monohydroperoxy octadecadienoates (HPODEs) that are then converted into diHPODEs. In contrast, we found that singlet oxygenation of conjugated HPODEs does not produce diHPODEs. Unconjugated HPODEs are unique products of singlet oxygenation of linoleate that are coproduced with conjugated HPODEs. Preparative separation of the mixture of regioisomeric mono and diHPODEs generated by singlet oxygenation of linloeate is impractical. However, a simple tactic circumvented the problem. Thus, selective conversion of the undesired conjugated HPODEs into Diels-Alder adducts could be accomplished under mild conditions by reaction with N-phenyltriazolinedione. These adducts were readily removed, and the two remaining unconjugated HPODEs could then be easily isolated regioisomerically pure. Each of these was subsequently converted into a different, regioisomerically pure, diHPODE through further singlet oxygenation.

Aldehydes↗
PubMed2005

Relationship between symmetry of porphyrinic pi-conjugated systems and singlet oxygen (1Delta g) yields: low-symmetry tetraazaporphyrin derivatives.

We have investigated the excited-state properties and singlet oxygen ((1)Delta(g)) generation mechanism in phthalocyanines (4M; M = H(2), Mg, or Zn) and in low-symmetry metal-free, magnesium, and zinc tetraazaporphyrins (TAPs), that is, monobenzo-substituted (1M), adjacently dibenzo-substituted (2AdM), oppositely dibenzo-substituted (2OpM), and tribenzo-substituted (3M) TAP derivatives, whose pi conjugated systems were altered by fusing benzo rings. The S(1)(x) and S(1)(y) states (these lowest excited singlet states are degenerate in D(4)(h) symmetry) split in the low-symmetry TAP derivatives. The excited-state energies were quantitatively determined from the electronic absorption spectra. The lowest excited triplet (T(1)(x)) energies were also determined from phosphorescence spectra, while the second lowest excited triplet (T(1)(y)) states were evaluated by using the energy splitting between the T(1)(x) and T(1)(y) states previously reported (Miwa, H.; Ishii, K.; Kobayashi, N. Chem. Eur. J. 2004, 10, 4422-4435). The singlet oxygen quantum yields (Phi(Delta)) are strongly dependent on the pi conjugated system. In particular, while the Phi(Delta) value of 2AdH(2) is smallest in our system, that of 2OpH(2), an isomer of 2AdH(2), is larger than that of 4Zn, in contrast to the heavy atom effect. The relationship between the molecular structure and Phi(Delta) values can be transformed into a relationship between the S(1)(x) --> T(1)(y) intersystem crossing rate constant (k(ISC)) and the energy difference between the S(1)(x) and T(1)(y) states (DeltaE(S)(x)(T)(y)). In each of the Zn, Mg, and metal-free compounds, the Phi(Delta)/tau(F) values (tau(F): fluorescence lifetime), which are related to the k(ISC) values, are proportional to exp(-DeltaE(S)(x)(T)(y)), indicating that singlet oxygen ((1)Delta(g)) is produced via the T(1)(y) state and that the S(1)(x) --> T(1)(y) ISC process follows the energy-gap law. From the viewpoint of photodynamic therapy, our methodology, where the Phi(Delta) value can be controlled by changing the symmetry of pi conjugated systems without heavy elements, appears useful for preparing novel photosensitizers.

Electrons↗
PubMed2004

Light- and singlet oxygen-mediated antifungal activity of phenylphenalenone phytoalexins.

The light-induced singlet oxygen production and antifungal activity of phenylphenalenone phytoalexins isolated from infected banana plants (Musa acuminata) are reported. Upon absorption of light energy all studied phenylphenalenones sensitise the production of singlet oxygen in polar and non-polar media. Antifungal activity of these compounds towards Fusarium oxysporum is enhanced in the presence of light. These results, together with the correlation of IC50 values under illumination with the quantum yield of singlet oxygen production and the enhancing effect of D2O on the antifungal activity, suggest the intermediacy of singlet oxygen produced by electronic excitation of the phenylphenalenone phytoalexins.

Antifungal Agents↗
PubMed2000

Effects of singlet oxygen on membrane sterols in the yeast Saccharomyces cerevisiae.

Photodynamic treatment of the yeast Saccharomyces cerevisiae with the singlet oxygen sensitizer toluidine blue and visible light leads to rapid oxidation of ergosterol and accumulation of oxidized ergosterol derivatives in the plasma membrane. The predominant oxidation product accumulated was identified as 5alpha, 6alpha-epoxy-(22E)-ergosta-8,22-dien-3beta,7a lpha-diol (8-DED). 9(11)-dehydroergosterol (DHE) was identified as a minor oxidation product. In heat inactivated cells ergosterol is photooxidized to ergosterol epidioxide (EEP) and DHE. Disrupted cell preparations of S. cerevisiae convert EEP to 8-DED, and this activity is abolished in a boiled control indicating the presence of a membrane associated enzyme with an EEP isomerase activity. Yeast selectively mobilizes ergosterol from the intracellular sterol ester pool to replenish the level of free ergosterol in the plasma membrane during singlet oxygen oxidation. The following reaction pathway is proposed: singlet oxygen-mediated oxidation of ergosterol leads to mainly the formation of EEP, which is enzymatically rearranged to 8-DED. Ergosterol 7-hydroperoxide, a known minor product of the reaction of singlet oxygen with ergosterol, is formed at a much lower rate and decomposes to give DHE. Changes of physical properties of the plasma membrane are induced by depletion of ergosterol and accumulation of polar derivatives. Subsequent permeation of photosensitizer through the plasma membrane into the cell leads to events including impairment of mitochondrial function and cell inactivation.

Cell Membrane↗
PubMed2000

p38 mitogen-activated protein kinase mediates bid cleavage, mitochondrial dysfunction, and caspase-3 activation during apoptosis induced by singlet oxygen but not by hydrogen peroxide.

p38 mitogen-activated protein kinase is activated and involved in cleavage of caspase-3 during apoptosis induced by a number of stimuli. However, the signaling events triggered by p38 that result in caspase-3 activation are still unknown. In human leukemia cells, two reactive oxygen species, singlet oxygen and hydrogen peroxide (H(2)O(2)), selectively stimulated the phosphorylation of p38. Preincubation of cells with SB203580, a specific inhibitor of p38, dose dependently inhibited DNA fragmentation induced by singlet oxygen but not by H(2)O(2). Protection from apoptosis by SB203580 correlated with inhibition of caspase-3, and several events that are associated with caspase-3 activation, including Bid cleavage, decrease in mitochondrial transmembrane potential and release of cytochrome c from mitochondria, whereas caspase-8 cleavage was not affected by this inhibitor. In contrast, blockade of caspase-8 with Ile-Glu-Thr-Asp-fluoromethyl ketone is sufficient to prevent formation of DNA fragments and to inhibit all the above signaling events, with exception of p38 phosphorylation, in both singlet oxygen- and H(2)O(2)-treated cells. These data suggest that caspase-3 activation is regulated through redundant signaling pathways that involve p38 and caspase-8 acting upstream of Bid during singlet oxygen-induced apoptosis, whereas the activation of caspase-3 by H(2)O(2) is only governed by a caspase-8-mediated apoptotic pathway.

Apoptosis↗
PubMed2000

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↗
PubMedDate not supplied

Pro-oxidating properties of melatonin in the in vitro interaction with the singlet oxygen.

In an aqueous system, the oxidation of the erythrocyte membrane by the singlet oxygen formed during the photoactivation of the rose bengal coloring was examined. The effects of the singlet oxygen on lipids and proteins were studied through the simultaneous quantification of peroxidation products, lipoperoxides and carbonyl groups, the oxidation of protein SH groups and the activity of the glyceraldehyde 3-phosphate dehydrogenase (G3PD) associated with the erythrocyte membrane. The antioxidant activity of melatonin was tested and compared to that of two antioxidants in extreme cases of hydrosolubility, ascorbate and beta-carotene, with the purpose of comparing the protective ability of melatonin against singlet oxygen. The results show the expected effect even at low (0.125-0.75 mM; 0.015-0.90 mM, respectively) for ascorbate and beta-carotene, antioxidants known to possess important antioxidant qualities against singlet oxygen. It is shown that melatonin, under the conditions described, and at the concentrations at which the other two compounds are efficacious, not only confers little antioxidant protection, but that a pro-oxidant tendency was proven both on lipids and proteins, as well as on G3PD enzymatic activity. The results show that the antioxidant protective effect that melatonin can exert on biological systems is probably not by a direct interaction with oxidant species, but probably, as has been previously proposed, through the regulation of antioxidant defense systems. The formation of secondary oxidation products, such as melatonin-derived endoperoxides, may explain the evidence found on pro-oxidant qualities of this molecule.

Adult↗
PubMed2004

Singlet oxygen production in photosynthesis.

A photosynthetic organism is subjected to photo-oxidative stress when more light energy is absorbed than is used in photosynthesis. In the light, highly reactive singlet oxygen can be produced via triplet chlorophyll formation in the reaction centre of photosystem II and in the antenna system. In the antenna, triplet chlorophyll is produced directly by excited singlet chlorophyll, while in the reaction centre it is formed via charge recombination of the light-induced charge pair. Changes of the mid-point potential of the primary quinone acceptor in photosystem II modulate the pathway of charge recombination in photosystem II and influence the yield of singlet oxygen production. Singlet oxygen can be quenched by beta-carotene, alpha-tocopherol or can react with the D1 protein of photosystem II as target. If not completely quenched, it can specifically trigger the up-regulation of the expression of genes which are involved in the molecular defence response of plants against photo-oxidative stress.

Chlorophyll↗
PubMed2005

Melatonin generates singlet oxygen on laser irradiation but acts as a quencher when irradiated by lamp photolysis.

Melatonin, a naturally occurring chemical mediator, although assigned a diverse range of functions, has attracted interest in recent years because of its ability to function as a free radical scavenger. Because of the implications of singlet oxygen in neurotoxicity, the objective of the study was to investigate the ability of melatonin to quench singlet oxygen generated using laser irradiation or lamp photolysis. The results show that melatonin produces radicals upon laser irradiation while the lamp photolysis studies show that melatonin is able to scavenge singlet oxygen produced by naphthalene. While melatonin is a free radical scavenger under biological conditions, it acts as a generator of singlet oxygen and or radicals (as PhiDelta is 1.41) when irradiated with laser light, implying that it has the potential to be used in photodynamic therapy in the destruction of tumors.

Benzofurans↗
PubMed1990

Scavenging of singlet molecular oxygen by imidazole compounds: high and sustained activities of carboxy terminal histidine dipeptides and exceptional activity of imidazole-4-acetic acid.

Singlet molecular oxygen was generated by illumination of phenosafranin in phosphate buffer at pH 7.5. Relative efficiencies of various imidazole compounds to form endoperoxides were assayed by following at 25 degrees C the rate of light- and imidazole-dependent bleaching of N,N-dimethyl-4-nitrosoaniline. Of over 30 imidazole compounds tested, imidazole-4-acetic acid, a major catabolite of histamine in mammals, exhibited the highest activity. L-Carnosine (beta-alanyl-L-histidine), a natural dipeptide prevalent in striated muscle of mammals, possessed several properties important for a physiologically significant scavenger of singlet oxygen. On a molar basis, this readily water-soluble C-terminal histidine dipeptide reacted with singlet oxygen two- to four-fold faster than free L-histidine and approximately two-fold faster than the N-terminal L-histidine dipeptides tested. Furthermore scavenging ability of L-carnosine did not appreciably increase or decrease with time of reaction, in contrast to behaviors exhibited by a number of other imidazole compounds that included some other C-terminal L-histidine dipeptides. The fungal metabolite, ergothioneine, blocked singlet oxygen generation by illuminated phenosafranin.

Carnosine↗