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Singlet Oxygen (singlet + oxygen)
Terms modified by Singlet Oxygen Selected AbstractsDiastereoselective Reactions of the Tiglic Acid Functionality Mediated by Oxazolidine Chiral Auxiliaries: A Mechanistic Comparison of DMD andm -CPBA Epoxidations versus Singlet Oxygen and PTAD Ene ReactionsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2005Aurelia Pastor Abstract 2,2-Dimethyloxazolidines have been utilized as chiral auxiliaries for the diastereoselective functionalization of the optically active tiglic acid derivatives (S)- 1 by means of epoxidation with DMD or m -CPBA and ene reactions with 1O2 or PTAD. In the DMD and m -CPBA epoxidations, high diastereoselectivities but opposite senses of diastereomer selection were observed. In contrast, the stereochemistry of the 1O2 and PTAD ene reactions depended on the size of the attacking enophile: whereas essentially perfect diastereoselectivity was obtained with PTAD, much lower stereoselection was observed with 1O2. The stereochemical results for the DMD and m -CPBA epoxidations and the PTAD ene reaction are explained in terms of the energy differences for the corresponding diastereomeric transition states, dictated by steric and electronic effects. The PTAD ene reaction for these tiglic acids (S)- 1 provides, after removal of the chiral auxiliaries, an attractive synthetic route for optically active ,-amino acid derivatives.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Quenching of Singlet Oxygen by Tertiary Aliphatic Amines.HELVETICA CHIMICA ACTA, Issue 10 2006Products, Structural Effects on Rates Abstract A kinetic and product study of the reaction of a series of , -methyl-substituted N -methylpiperidines with thermally generated 1O2 in MeCN was carried out. It was found that as the number of , -methyl groups (Me in , -position relative to the N-atom) increases, the rate of 1O2 quenching (physical plus chemical) slightly decreases. This finding shows that, with respect to the reaction rate, steric effects are much more important than electronic effects as the latter should have produced the opposite result. The opposite outcome was instead found for the chemical quenching that leads to the N -demethylation products and N -formyl derivatives. The same trend was observed for the ratio between N -demethylation and formation of the N -formyl derivatives (NH/NCHO ratio). All these results are consistent with the mechanism reported in Scheme,1 where an exciplex is first formed that by a H-atom transfer process produces an , -amino-substituted C-radical. The latter forms the product of N -demethylation by one electron oxidation, or affords the N -formyl derivative by radical coupling (Scheme,1). Similar results were obtained with N,N -dimethylcyclohexanamine. However, this ,acyclic' amine exhibited behaviors quite distinct from those of the N -methylpiperidines series, with respect to reaction rate, extent of chemical quenching, and NH/NCHO ratio. [source] Effect of the Media on the Quantum Yield of Singlet Oxygen (O2(1,g)) Production by 9H -Fluoren-9-one: Solvents and Solvent MixturesHELVETICA CHIMICA ACTA, Issue 2 2003Claudia We have investigated the effect of a series of 18 solvents and mixtures of solvents on the production of singlet molecular oxygen (O2(1,g), denoted as 1O2) by 9H -fluoren-9-one (FLU). The normalized empirical parameter E derived from ET(30) has been chosen as a measure of solvent polarity using Reichardt's betaine dyes. Quantum yields of 1O2 production (,,) decrease with increasing solvent polarity and protic character as a consequence of the decrease of the quantum yield of intersystem crossing (,ISC). Values of ,, of unity have been found in alkanes. In nonprotic solvents of increasing polarity, ,ISC and, therefore, ,, decrease due to solvent-induced changes in the energy levels of singlet and triplet excited states of FLU. This compound is a poor 1O2 sensitizer in protic solvents, because hydrogen bonding considerably increases the rate of internal conversion from the singlet excited state, thus diminishing ,, to values much lower than those in nonprotic solvents of similar polarity. In mixtures of cyclohexane and alcohols, preferential solvation of FLU by the protic solvent leads to a fast decrease of ,, upon addition of increasing amounts of the latter. [source] Kinetic Study of the Quenching Reaction of Singlet Oxygen by Common Synthetic Antioxidants (tert -Butylhydroxyanisol, tert -di-Butylhydroxytoluene, and tert -Butylhydroquinone) as Compared with ,-TocopherolJOURNAL OF FOOD SCIENCE, Issue 5 2009Ji In Kim ABSTRACT:, Effects of synthetic phenolic antioxidants (BHA, BHT, and TBHQ) on the methylene blue (MB) sensitized photooxidation of linoleic acid as compared with that of ,-tocopherol have been studied. Their antioxidative mechanism was studied by both ESR spectroscopy in a 2,2,6,6-tetramethylpiperidone (TMPD)-methylene blue (MB) system and spectroscopic analysis of rubrene oxidation induced by a chemical source of singlet oxygen. Total singlet oxygen quenching rate constants (kox,Q+kq) were determined using a steady state kinetic equation. TBHQ showed the strongest protective activity against the MB sensitized photooxidation of linoleic acid, followed by BHA and BHT. TBHQ (1 × 10,3 M) exhibited 86.5% and 71.4% inhibition of peroxide and conjugated diene formations, respectively, in linoleic acid photooxidation after 60-min light illumination. The protective activity of TBHQ against the photosensitized oxidation of linoleic acid was almost comparable to that of ,-tocopherol. The data obtained from ESR and rubrene oxidation studies clearly showed the strong singlet oxygen quenching ability of TBHQ. The kox,Q+kq of BHA, BHT, and TBHQ were determined to be 3.37 × 107, 4.26 × 106, and 1.67 × 108 M,1 s,1, respectively. The kox,Q+kq of TBHQ was within the same order of magnitude of that of ,-tocopherol, a known efficient singlet oxygen quencher. There was a high negative correlation (r2,=,,0.991) between log (kox,Q+kq) and reported oxidation potentials for the synthetic antioxidants, indicating their charge-transfer mechanism for singlet oxygen quenching. This is the 1st report on the kinetic study on kox,Q+kq of TBHQ in methanol as compared with other commonly used commercial synthetic antioxidants and ,-tocopherol. [source] Involvement of Singlet Oxygen in the Solid-State Photochemistry of P3HTMACROMOLECULAR RAPID COMMUNICATIONS, Issue 22 2008Matthieu Manceau Abstract We studied the role that singlet oxygen plays in the solid-state photochemistry of poly(3-hexylthiophene) (P3HT). The photosensitized formation of singlet oxygen by solid-state P3HT and its subsequent reactivity on the polymer were investigated. Using a fluorescent probe, it was found that singlet oxygen (1O2) could be produced by irradiation of P3HT by photosensitization, with no oxidation of the polymer. In addition, 1O2 was directly formed on P3HT via a chemical reaction, again with no oxidation of the polymer. These results give strong evidence that 1O2 is not the principal photo-oxidative degradation intermediate of P3HT, which conflicts with previous reports. [source] Spatial Distribution of Protein Damage by Singlet Oxygen in KeratinocytesPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2008Yu-Ying He Singlet oxygen may be generated in cells by either endogenous or exogenous photosensitizers as a result of exposure to UV or visible irradiation. We have used immuno-spin trapping (Free Radic. Biol. Med. 36: 1214, 2004) to identify the subcellular targets of singlet oxygen generated by rose bengal (RB). Confocal fluorescence microscopy of HaCaT keratinocytes incubated with RB clearly showed that the dye entered the cells and was located mainly in the perinuclear region, probably associated with the Golgi apparatus and endoplasmic reticulum. Previous studies by Wright et al. (Free Radic. Biol. Med.34: 637, 2003) have shown that long-lived protein hydroperoxides (POOH) are present in cells exposed to singlet oxygen-generating dyes. The addition of reducing metal ions such as Cu+ to POOH results in the generation of protein-derived radicals, POO, and PO,, which react with the spin trap 5,5-dimethyl-1-pyrroline N -oxide (DMPO) to give relatively stable spin adducts. In order to determine the subcellular localization of the protein-DMPO adducts, we exposed keratinocytes to RB/light exposure and then incubated the cells with Cu+ and DMPO. After staining with antibody against DMPO followed by a secondary Alexa Fluor 488 goat anti-rabbit IgG, the intracellular distribution of protein-DMPO adducts was determined by confocal microscopy. The subcellular localization of the protein DMPO adducts was coincident with that of RB. This approach may provide information on the spatial distribution of singlet oxygen generated in cells. [source] Bacteriochlorophyll e Monomers, but Not Aggregates, Sensitize Singlet Oxygen: Implications for a Self-photoprotection Mechanism in Chlorosomes,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2002Juan B. Arellano ABSTRACT Sensitization of singlet delta oxygen (O2(1,g)) by bacteriochlorophyll e (BChle) has been investigated to gain a better understanding of the photoprotection mechanism(s) operating in chlorosomes of green photosynthetic bacteria. The sensitization process has been studied in media where BChle forms monomers (acetone and aqueous solutions containing 0.5% Triton X-100 [TX]) and in systems where BChle aggregates, namely, aqueous solutions containing 0.003% monogalactosyl diglyceride (MGDG) and chlorosomes (control as well as hexanol perturbed) from Chlorobium phaeobacteroides strain CL1401. In Ar-purged acetone, BChle triplets (BChle,) have a lifetime of a few tens of microseconds; however, in air-saturated acetone, quenching of BChle, by ground-state oxygen (O2(3,,g)) and formation of O2(1,g) take place. The O2(1,g) so formed is susceptible to quenching by BChle0, a ground-state BChle molecule. A Stern,Volmer analysis reveals a linear fit between the decay rate of O2(1,g) and the BChle concentration. The rate constants for the quenching of O2(1,g) by BChle0 and for the deactivation of O2(1,g) by the solvent come out to be kq= (1.4 ± 0.1) × 109 M,1 s,1 and k0= (18.5 ± 0.7) × 103 s,1, respectively. The absolute quantum yield of O2(1,g) sensitization by BChle monomers is 0.65 ± 0.15 in air-saturated acetone. In aqueous phase, the triplet lifetime of BChle aggregates in native or hexanol-perturbed chlorosomes shortens by more than two orders of magnitude when compared with the triplet lifetime of BChle monomers in 0.5% TX solution (a few hundreds of microseconds). Quenching by carotenoids (Car) makes only a minor contribution to the decay of BChle, in aggregates. Because O2(1,g) sensitization by BChle, could be detected neither in MGDG aggregates nor in chlorosomes (control as well as hexanol perturbed), it is concluded that (1) this process is highly likely when BChle is present as a monomer but not when it is tightly packed in artificial aggregates or in chlorosomes; and (2) Car, though vital for the baseplate BChla, are dispensable for BChle. [source] Singlet Oxygen, but not Oxidizing Radicals, Induces Apoptosis in HL-60 Cells,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2000Irene E. Kochevar ABSTRACT Oxidizing species (OS), produced by photosensitization or derived from cytotoxic agents, activate apoptotic pathways. We investigated whether two different OS, formed at the same subcellular sites, have equivalent ability to initiate apoptosis in HL-60 cells. Our previous work showed that absorption of visible light by rose bengal (RB) produces singlet oxygen exclusively, whereas absorption of ultraviolet A produces RB-derived radicals in addition to singlet oxygen. Singlet oxygen, but not the RB-derived radicals, induced nuclear condensation and DNA fragmentation into nucleosome-size fragments in a dose dependent manner. In contrast, the RB-derived radicals caused greater lipid oxidation than singlet oxygen. These results indicate that different OS, produced at the same subcellular sites, do not have the same ability to induce apoptosis and that the ability of an OS to initiate lipid oxidation does not necessarily correlate with its ability to induce apoptosis. [source] ChemInform Abstract: Highly Efficient Oxidation of Amines to Imines by Singlet Oxygen and Its Application in Ugi-Type Reactions.CHEMINFORM, Issue 11 2010Gaoxi Jiang Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Reaction of Electron-Deficient N=N, N=O Double Bonds, Singlet Oxygen, and CC Triple Bonds with Acyloxyketenes or Mesoionic 1,3-Dioxolium-4-olates: Generation of Unstable Mesoionic 1,3-Dioxolium-4-olates from Acyloxyketenes.CHEMINFORM, Issue 26 2007Masashi Hamaguchi Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Reversible 1,4-Cycloaddition of Singlet Oxygen to N-Substituted 2-Pyridones: 1,4-Endoperoxide as a Versatile Chemical Source of Singlet Oxygen.CHEMINFORM, Issue 19 2005Masakatsu Matsumoto No abstract is available for this article. [source] Regioselectivity in the Ene Reaction of Singlet Oxygen with ortho-Prenylphenol Derivatives.CHEMINFORM, Issue 44 2003Jean-Jacques Helesbeux Abstract For Abstract see ChemInform Abstract in Full Text. [source] 9,10-Diarylanthracenes as Molecular Switches: Syntheses, Properties, Isomerisations and Their Reactions with Singlet OxygenCHEMISTRY - A EUROPEAN JOURNAL, Issue 36 2008Daniel Zehm Abstract A series of 9,10-diarylanthracenes with various substituents at the ortho positions have been synthesised by palladium-catalysed cross-coupling reactions. Such compounds exhibit interesting physical properties and can be applied as molecular switches. Despite the high steric demand of the substituents, products were formed in moderate-to-good yields. In some cases, microwave conditions further improved yields. Bis-coupling afforded two isomers (syn and anti) that do not interconvert at room temperature. These products were easily separated and their relative stereochemistries were unequivocally assigned by NMR spectroscopy and X-ray analysis. The syn and anti isomers exhibit different physical properties (e.g., melting points and solubilities) and interconversion by rotation around the aryl,aryl axis commences at <100,°C for fluoro-substituted diarylanthracenes and at >300,°C for alkyl- or alkoxy-substituted diarylanthracenes. The reactions with singlet oxygen were studied separately and revealed different reactivities and reaction pathways. The yields and reactivities depend on the size and electronic nature of the substituents. The anti isomers form the same 9,10-endoperoxides as the syn species, occasionally accompanied by unexpected 1,4-endoperoxides as byproducts. Thermolysis of the endoperoxides exclusively yielded the syn isomers. The interesting rotation around the aryl,aryl axis allows the application of 9,10-diarylanthracenes as molecular switches, which are triggered by light and air under mild conditions. Finally, the oxygenation and thermolysis sequence provides a simple, synthetic access to a single stereoisomer (syn) from an unselective coupling step. [source] Chemistry and Reaction of Singlet Oxygen in FoodsCOMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY, Issue 2 2002D. B. Min ABSTRACT Singlet oxygen is a highly reactive, electrophilic, and nonradical molecule. It is different from diradical triplet oxygen in its electron arrangement. Photosensitizers can form singlet oxygen from triplet oxygen in the presence of light. The reaction rate of singlet oxygen with foods is much greater than that of triplet oxygen due to the low activation energy. Singlet oxygen oxidation produces undesirable compounds in foods during processing and storage. However, carotenoids and tocopherols in foods can minimize singlet oxygen oxidation. The in-depth scientific knowledge on the formation, reactions, quenching mechanisms, and kinetics of singlet oxygen can greatly improve the quality of foods by minimizing the oxidation during processing and storage. The single oxygen oxidation of foods has contributed to the explanation of several important chemical reactions in the reversion flavor in soybean oil, sunlight flavor in milk products, and the rapid losses of vitamin D, riboflavin, and ascorbic acid in milk under light storage. [source] Rapid determination of rice seed vigour by spontaneous chemiluminescence and singlet oxygen generation during early imbibitionLUMINESCENCE: THE JOURNAL OF BIOLOGICAL AND CHEMICAL LUMINESCENCE, Issue 1 2003Wenli Chen Abstract Using a highly sensitive single photon counter, a spontaneous chemiluminescence (CL) study on rice (Oryza sativa L.) seeds stored in different years was carried out. We first observed that the degree of ageing in rice seeds was related to the intensity of spontaneous CL during early imbibition (0,30 min). Rice seeds stored for a shorter time had a stronger intensity of CL in early imbibition. The germination rate of rice seeds showed an obvious positive correlation with the intensity of spontaneous CL. Singlet oxygen (1O2) in rice seeds during early imbibition was investigated by a CL method using a cypridina luciferin analogue, 2-methyl-6-(p -methoxyphenyl)-3,7-dihydroimidazo [1,2,] pyrazin-3-one (MCLA), as a selective CL probe. Additional experimental evidence for the formation of 1O2 came from the quenching effect of sodium azide (NaN3) on MCLA-mediated rice seeds' CL. Analysis based on the experimental results demonstrated that spontaneous CL in rice seeds during early imbibition was mainly contributed by singlet oxygen (1O2). Copyright © 2002 John Wiley & Sons, Ltd. [source] Primary Photophysical Properties of Moxifloxacin, A Fluoroquinolone AntibioticPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 5 2008Fernando Lorenzo The photophysical properties of the fluoroquinolone antibiotic moxifloxacin (MOX) were investigated in aqueous media. MOX in water, at pH 7.4, shows two intense absorption bands at 287 and 338 nm (, = 44 000 and 17 000 dm3 mol,1 cm,1, respectively). The absorption and emission properties of MOX are pH-dependent, pKa values for the protonation equilibria of both the ground (6.1 and 9.6) and excited singlet states (6.8 and 9.1) of MOX were determined spectroscopically. MOX fluoresces weakly, the quantum yield for fluorescence emission being maximum (0.07) at pH 8. Phosphorescence from the excited triplet state in frozen ethanol solution has a quantum yield of 0.046. Laser flash photolysis and pulse radiolysis studies have been carried out to characterize the transient species of MOX in aqueous solution. On laser excitation, MOX undergoes monophotonic photoionization with a quantum yield of 0.14. This leads to the formation of a long-lived cation radical whose absorption is maximum at 470 nm (,470 = 3400 dm3 mol,1 cm,1). The photoionization process releases hydrated electron which rapidly reacts (k = 2.8 × 1010 dm3 mol,1 s,1) with ground state MOX, yielding a long-lived anion radical with maximum absorption at 390 nm (,390 = 2400 dm3 mol,1 cm,1). The cation radical of MOX is able to oxidize protein components tryptophan and tyrosine. The bimolecular rate constants for these reactions are 2.3 × 108 dm3 mol,1 s,1 and 1.3 × 108 dm3 mol,1 s,1, respectively. Singlet oxygen sensitized by the MOX triplet state was also detected only in oxygen-saturated D2O solutions, with a quantum yield of 0.075. [source] Spatial Distribution of Protein Damage by Singlet Oxygen in KeratinocytesPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2008Yu-Ying He Singlet oxygen may be generated in cells by either endogenous or exogenous photosensitizers as a result of exposure to UV or visible irradiation. We have used immuno-spin trapping (Free Radic. Biol. Med. 36: 1214, 2004) to identify the subcellular targets of singlet oxygen generated by rose bengal (RB). Confocal fluorescence microscopy of HaCaT keratinocytes incubated with RB clearly showed that the dye entered the cells and was located mainly in the perinuclear region, probably associated with the Golgi apparatus and endoplasmic reticulum. Previous studies by Wright et al. (Free Radic. Biol. Med.34: 637, 2003) have shown that long-lived protein hydroperoxides (POOH) are present in cells exposed to singlet oxygen-generating dyes. The addition of reducing metal ions such as Cu+ to POOH results in the generation of protein-derived radicals, POO, and PO,, which react with the spin trap 5,5-dimethyl-1-pyrroline N -oxide (DMPO) to give relatively stable spin adducts. In order to determine the subcellular localization of the protein-DMPO adducts, we exposed keratinocytes to RB/light exposure and then incubated the cells with Cu+ and DMPO. After staining with antibody against DMPO followed by a secondary Alexa Fluor 488 goat anti-rabbit IgG, the intracellular distribution of protein-DMPO adducts was determined by confocal microscopy. The subcellular localization of the protein DMPO adducts was coincident with that of RB. This approach may provide information on the spatial distribution of singlet oxygen generated in cells. [source] Singlet Oxygen, but not Oxidizing Radicals, Induces Apoptosis in HL-60 Cells,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2000Irene E. Kochevar ABSTRACT Oxidizing species (OS), produced by photosensitization or derived from cytotoxic agents, activate apoptotic pathways. We investigated whether two different OS, formed at the same subcellular sites, have equivalent ability to initiate apoptosis in HL-60 cells. Our previous work showed that absorption of visible light by rose bengal (RB) produces singlet oxygen exclusively, whereas absorption of ultraviolet A produces RB-derived radicals in addition to singlet oxygen. Singlet oxygen, but not the RB-derived radicals, induced nuclear condensation and DNA fragmentation into nucleosome-size fragments in a dose dependent manner. In contrast, the RB-derived radicals caused greater lipid oxidation than singlet oxygen. These results indicate that different OS, produced at the same subcellular sites, do not have the same ability to induce apoptosis and that the ability of an OS to initiate lipid oxidation does not necessarily correlate with its ability to induce apoptosis. [source] Singlet oxygen inhibits nonradiative defects in porous siliconPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 6 2009V. B. Pikulev Abstract Experimental evidences are presented for the first time that singlet oxygen generated ex situ acts as an inhibitor of nonradiative recombination in porous silicon (PSi). This effect is observed on a pristine PSi as well as on degraded porous layers quenched by ozone adsorption. A photoluminescence (PL) enhancement produced by singlet oxygen is accompanied with only slight oxidation of a PSi. We assume that the observed effect on PL efficiency is due to gentle selective oxidation of single defects on silicon nanocrystal surface. (© 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Chemistry and Reaction of Singlet Oxygen in FoodsCOMPREHENSIVE REVIEWS IN FOOD SCIENCE AND FOOD SAFETY, Issue 2 2002D. B. Min ABSTRACT Singlet oxygen is a highly reactive, electrophilic, and nonradical molecule. It is different from diradical triplet oxygen in its electron arrangement. Photosensitizers can form singlet oxygen from triplet oxygen in the presence of light. The reaction rate of singlet oxygen with foods is much greater than that of triplet oxygen due to the low activation energy. Singlet oxygen oxidation produces undesirable compounds in foods during processing and storage. However, carotenoids and tocopherols in foods can minimize singlet oxygen oxidation. The in-depth scientific knowledge on the formation, reactions, quenching mechanisms, and kinetics of singlet oxygen can greatly improve the quality of foods by minimizing the oxidation during processing and storage. The single oxygen oxidation of foods has contributed to the explanation of several important chemical reactions in the reversion flavor in soybean oil, sunlight flavor in milk products, and the rapid losses of vitamin D, riboflavin, and ascorbic acid in milk under light storage. [source] Electrochemical Monitoring of Singlet Oxygen ProductionELECTROANALYSIS, Issue 21 2009Duncan Sharp Abstract The exploitation of singlet oxygen generating compounds as a means of targeted therapies drives the need to develop methods for assessing the efficacy of such compounds and their capacity for generating the reactive oxygen species. Degradation of diphenylisobenzofuran by singlet oxygen is widely used as a spectroscopic probe but its application can be problematic. An alternative detection strategy exploiting the electrochemical monitoring of the quencher concentration, by square wave voltammetry, has been shown to provide a more sensitive and flexible option that could be used to address the increasing interest in photosensitizing materials. [source] Photodynamic therapy against cyanobacteriaENVIRONMENTAL TOXICOLOGY, Issue 1 2007M. Drábková Abstract This study explores the use of photosensitizers and reactive oxygen species (ROS) to limit growth of cyanobacteria. We chose 12 phthalocyanines, tetraphenol porphyrine, and methylene blue as compounds producing singlet oxygen. Hydrogen peroxide was chosen as another source of ROS. These compounds were tested using algal toxicity tests in microplates on three cultures of green algae (Pseudokirchneriella subcapitata, Scenedesmus quadricauda, and Chlorella kessleri) and on three cultures of cyanobacteria (Synechococcus nidulans, Microcystis incerta, and Anabaena sp.). Results indicate that photosensitizers and singlet oxygen could be highly toxic for some selected phytoplankton species. Green alga Scenedesmus quadricauda was highly sensitive (EC50 = 0.07 mg/L) to compounds producing singlet oxygen, although it was not sensitive to hydrogen peroxide, which was about 10 times more toxic for cyanobacteria. We conclude that the compounds producing hydroxyl radical species seems to be more promising to treat cyanobacterial blooms than the compounds producing the singlet oxygen. © 2007 Wiley Periodicals, Inc. Environ Toxicol 22: 112,115, 2007. [source] Effect of sunlight exposure and aging on skin surface lipids and urateEXPERIMENTAL DERMATOLOGY, Issue 2003Nobumasa Hayashi Abstract Free fatty acids (FFA), squalene, squalene hydroperoxide, and uric acid in the methanol extracts from human skin surface were measured. Levels of FFA and squalene were significantly lower in the older (83.7 ± 9.4 years) than in the younger (22.2 ± 3.9 years) group. FFA are mostly saturated, and linoleic acid is an exclusive polyunsaturated fatty acid. The composition of linoleic acid decreased in the older group by 40%, suggesting age-dependent loss of oxidatively vulnerable polyunsaturated fatty acid. Even monounsaturated acids such as palmitoleic and oleic acids decreased significantly in the older group. This could be interesting because 2-nonenal is the oxidation product of palmitoleic acid and has been identified as the major aged body odor component. Sunlight exposure for 1.5 h did not change levels of FFA and squalene, or FFA composition. However, squalene hydroperoxide increased by 60-fold, as reported previously, suggesting that hydroperoxide is produced by singlet oxygen. Uric acid increased by two-fold, which may be the adaptive response against photo-oxidative stress because uric acid is a good scavenger of singlet oxygen and oxygen radicals. [source] Effects of singlet oxygen on membrane sterols in the yeast Saccharomyces cerevisiaeFEBS JOURNAL, Issue 6 2000Till Böcking 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 5,,6,-epoxy-(22E)-ergosta-8,22-dien-3,,7,-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. [source] Cover Picture: Spectroscopic and Photophysical Properties of a Highly Derivatized C60 Fullerol (Adv. Funct.ADVANCED FUNCTIONAL MATERIALS, Issue 1 2006Mater. Abstract The photo-oxidative stress in aqueous milieus can readily be generated in the presence of newly synthesized highly derivatized fullerenes (fullerols) reported in the Full Paper by Vileno and co-workers on p.,120. Their basic structural and photophysical properties were characterized using a range of methods, including X-ray photoelectron and IR spectroscopies, and electron spin resonance. Moreover, a significant drop of the local stiffness of a living cell was monitored using atomic force microscopy. This cell softening was attributed to the early effects of the photo-oxidative stress. Hydroxylated C60 molecules, also called fullerols, are a class of water-soluble fullerenes. Here we report the synthesis in acidic conditions of a highly derivatized fullerol (up to 36 carbons per C60 are oxidized). Spectroscopic investigations (X-ray photoelectron spectroscopy and infrared absorption) highlight the coexistence of both acidic and basic forms for the hydroxyl addends of derivatized C60. pH titrimetry reveals that, at millimolar concentrations, only ten protons per fullerol molecule are labile. Such a low value, as compared to 36 hydroxyl groups, is explained by the formation of clusters. A UV-vis absorption study performed over a large range of concentrations also points to the aggregation phenomenon. Moreover, this study shows that the clusters of fullerols appear at relatively low (micromolar) concentrations. An electron spin resonance (ESR) study, based on the attack of singlet oxygen (1,g) on 2,2,6,6-tetramethyl-4-piperidinol (TMP-OH), has proved the potential of hydroxylated C60 for performing efficient generation of singlet oxygen in aqueous solution. ESR measurements, which allow detection and quantification of 1,g, have also revealed the generation of reactive oxygen species (ROS). The yield of generation of 1,g and ROS is strongly correlated to the concentration of fullerol, thus also pointing to the aggregation of fullerol molecules. Exposing glioblastoma cells to oxidative stress in the presence of hydroxylated C60 and visible light has also been performed. Atomic force microscopy is used to monitor the relevant diminishment of the Young's modulus values for cells exposed to the oxidative stress. These results point to a possible application field of fullerols for performing bio-oxidations. [source] Two Novel Antioxidative Stilbene Tetramers from Parthenocissus laetevirensHELVETICA CHIMICA ACTA, Issue 7 2009Shan He Abstract Laetevirenols F (1) and G (2), two novel stilbene tetramers with an unprecedented skeleton, were isolated from Parthenocissus laetevirens. Their structures were elucidated by spectroscopic analysis, including 1D- and 2D-NMR experiments, and their possible biogenetic pathway was discussed. In addition, both compounds were determined to be potent singlet-oxygen quenchers by electron paramagnetic resonance (EPR) experiments, which highlights their potential pharmacological applications in singlet oxygen mediated diseases. [source] Synthesis, DNA-Binding and Photocleavage Studies of the Ruthenium(II) Complexes [Ru(phen)2(ppd)]2+ and [Ru(phen)(ppd)2]2+ (ppd=Pteridino[6,7- f],[1,10]phenanthroline-11,13(10H,12H)-dione, phen=1,10-Phenanthroline)HELVETICA CHIMICA ACTA, Issue 3 2008Feng Gao Abstract Two new complexes, [Ru(phen)2(ppd)]2+ (1) and [Ru(phen)(ppd)2]2+ (2) (ppd=pteridino[6,7- f],[1,10]phenanthroline-11,13(10H,12H)-dione, phen=1,10-phenanthroline) were synthesized and characterized by ES-MS, 1H-NMR spectroscopy, and elemental analysis. The intercalative DNA-binding properties of 1 and 2 were investigated by absorption-spectroscopy titration, luminescence-spectroscopy studies, thermal denaturation, and viscosity measurements. The theoretical aspects were further discussed by comparative studies of 1 and 2 by means of DFT calculations and molecular-orbital theory. Photoactivated cleavage of pBR322 DNA by the two complexes were also studied, and 2 was found to be a much better photocleavage reagent than 1. The mechanism studies revealed that singlet oxygen and the excited-states redox potentials of the complex may play an important role in the DNA photocleavage. [source] Synthesis, DNA Binding, and DNA Photocleavage of the Ruthenium(II) Complexes [Ru(bpy)(btip)]2+ and [Ru(dmb)(btip)]2+ (bpy,=,2,2,-Bipyridine; btip,=,2-Benzo[b]thien-2-yl-1H -imidazo[4,5- f],[1,10]phenanthroline; dmb,=,4,4,-Dimethyl-2,2,-bipyridine)HELVETICA CHIMICA ACTA, Issue 1 2007Li-Feng Tan Abstract The new polypyridyl ligand btip (=,2-benzo[b]thien-2-yl-1H -imidazo[4,5- f],[1,10]phenanthroline) and its RuII complexes [Ru(bpy)2(btip)]2+ (1; bpy,=,2,2,-bipyridine) and [Ru(dmb)2(btip)]2+ (2; dmb,=,4,4,-dimethyl-2,2,-bipyridine) were synthesized and characterized by elemental analysis, MS, and 1H-NMR. The DNA-binding properties of the two complexes to calf-thymus DNA (CT-DNA) were investigated by different spectrophotometric methods and viscosity measurements. The results suggest that both complexes bind to CT-DNA through intercalation. Also, when irradiated at 400,nm, the two complexes promote the photocleavage of plasmid pBR-322 DNA. Thereby, under comparable experimental conditions, complex 1 cleaves DNA more effectively than complex 2 does. Mechanistic studies reveal that singlet oxygen (1O2) and hydroxyl radicals (OH.) play a significant role in the photocleavage. [source] Synthesis and Photochemical Evaluation of Iodinated Squarylium Cyanine DyesHELVETICA CHIMICA ACTA, Issue 5 2005Paulo Several (multiply) iodinated squarylium cyanine dyes of type 1 and 8 (see Scheme and Table), derived from 1,3-benzothiazole and 6-iodo-1,3-benzothiazole, were synthesized as potential new photosensitizers, with absorptions in the 700-nm region. Their ability to generate singlet oxygen (1O2) was assessed by luminescence-decay measurement in the near-IR. Some of these new dyes show interesting photophysical properties, and may be potentially used in photodynamic therapy (PDT). [source] Nanotechnologies: Tools for sustainability in a new wave of water treatment processesINTEGRATED ENVIRONMENTAL ASSESSMENT AND MANAGEMENT, Issue 4 2006Jean-Yves Bottero Abstract In the environmental technology industry alone, nanomaterials will enable new means of reducing the production of industrial wastes, using resources more sparingly, remediating industrial contamination, providing potable water, and improving the efficiency of energy production. This paper discusses three new kinds of nanotechnology materials that should be developed in the future: Membranes, oxidants, and adsorbents. Nanoscale control of membrane architecture may yield membranes of greater selectivity and lower cost in both water treatment and water fabrication. Fullerene-based oxidant nanomaterials such as C60 have a high electron affinity and reactivity, and are capable of producing reactive oxygen species such as singlet oxygen and superoxides. Fullerenes might be used in engineered systems to photocatalytically oxidize organic contaminants, or inhibit or inactivate microbes. The ability to tailor surfaces can help to increase adsorbing capacities or recognize specific contaminants. The potential environmental risks are that nanomaterials could interact with biota and that their toxicity adversely may affect ecosystems. As nanochemistry emerges as an important force behind new environmental technologies, we are also presented with the responsibility of considering the environmental implications of an emerging technology at its inception and taking every precaution to ensure that these technologies develop as tools of sustainability rather than becoming future liabilities. [source] | |||||||||||||||||||||||||