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PubMed2003

Antiphoto-oxidative activity of sesamol in methylene blue- and chlorophyll-sensitized photo-oxidation of oil.

The effects and mechanism of sesamol on the methylene blue- or chlorophyll-sensitized photo-oxidations of soybean oil have been studied. Sesamol showed strong antiphoto-oxidative activity in both methylene blue-and chlorophyll-sensitized photo-oxidations of soybean oil in a dose-dependent manner. The 1.0 x 10(-3) M sesamol treatments showed 84.7 and 43.4% inhibitions of methylene blue- and chlorophyll-sensitized photo-oxidations of soybean oil in methylene chloride. The antiphoto-oxidative activity of sesamol was comparable to that of delta-tocopherol in both methylene blue- and chlorophyll-sensitized photo-oxidations, at the same molar basis. Sesamol effectively inhibited rubrene oxidation with a chemical source of singlet oxygen in microemulsion, showing its strong singlet oxygen quenching ability. The results suggested that the antiphoto-oxidative activity of sesamol in the photo-oxidation of oil was, at least in part, due to its singlet oxygen scavenging activity. The singlet oxygen quenching rate constant (k(ox-Q) + k(q)) of sesamol was determined to be 1.9 +/- 0.3 x 10(7) M(-1) s(-1). This represents the first report on the antiphoto-oxidative activity of sesamol in the sensitized photo-oxidation of oil, and its bimolecular singlet oxygen quenching ability.

Antioxidants↗
PubMed2006

Effects, quenching mechanisms, and kinetics of water soluble compounds in riboflavin photosensitized oxidation of milk.

To protect the nutrient and flavor stability of milk under light, the effects of 0, 0.01, 0.03, and 0.05 M 1,4-diazabicyclo[2,2,2]octane (DABCO) and 2,5-dimethylfuran (DMF) on the riboflavin photosensitized oxidation of milk were studied. The oxidation of milk was studied by measuring the headspace oxygen in sample bottles after 3 h of light exposure at 3000 lux. As the concentration of DABCO and DMF, which are water soluble compounds, increased in the sample from 0, 0.01, and 0.03 to 0.05 M, the depleted headspace oxygen content significantly decreased (P < 0.05). Steady state kinetic studies of singlet oxygen oxidation showed that the antioxidant activity of DABCO and DMF was due to singlet oxygen quenching. The reaction rate constant of singlet oxygen with milk fat was 8.1 x 10(5) M(-1) s(-1). Total singlet oxygen quenching rates of DABCO and DMF were 1.5 x 10(7) and 2.6 x 10(7) M(-1) s(-1), respectively. DABCO and DMF could be used to slow the reaction between singlet oxygen and milk components to protect nutrients, especially riboflavin, and to improve the oxidative stability of milk fat during storage or processing under light.

Animals↗
PubMed2007

Photoinduced generation of 2,3-butanedione from riboflavin.

The volatile compound formation from riboflavin solution of a phosphate buffer (0.1 M, pH 6.5) under light for 15 h was studied by SPME-GC and SPME-GC/MS analysis. Only one major compound in the riboflavin solution was formed and increased as the light exposure time increased. The light-exposed riboflavin solution had a buttery odor. The compound of riboflavin solution under light was analyzed by gas chromatography and olfactometry. The major volatile compound eluted from the gas chromatograph had a buttery odor. The buttery odor compound was positively identified as 2,3-butanedione by a combination of gas chromatographic retention time, mass spectrum, and odor evaluation of authentic 2,3-butanedione. The addition of sodium azide, a singlet oxygen quencher, to riboflavin solution minimized the formation of the buttery odor compound. Singlet oxygen was involved in the formation of the buttery odor. The 2,3-butanedione was produced from the reaction between riboflavin and singlet oxygen. Singlet oxygen was formed from triplet oxygen by riboflavin photosensitization mechanism. This is the first reported oxidation reaction between riboflavin and singlet or triplet in food and biological systems.

Chromatography, Gas↗
PubMed2003

Polyoxometalate sensitization in mechanistic studies of photochemical reactions: the decatungstate anion as a reference sensitizer for photoinduced free radical oxygenations of organic compounds.

The photosensitized oxygenation of organic molecules plays a key role in numerous processes of biological and industrial significance, such as, for example, photodynamic action and photodegradation of polymers. These reactions proceed either via quenching by the substrate of photophysically generated singlet oxygen, O2(1deltag), or via addition of ground state oxygen to photochemically generated radicals derived from the substrate, or via both pathways. The evaluation of the contributions of both mechanisms to the overall process requires reference sensitizers that exclusively induce one of the corresponding reactions. Some compounds are known to produce singlet oxygen with unit efficiency, but no references to sensitizers producing free radicals but no singlet oxygen have been found so far. In this work, we propose to use the decatungstate anion, W10O32(4-), as a first reference sensitizer for free radical oxygenations of organic molecules. A combination of time-resolved and steady-state studies has been performed to compare the photo-oxygenation of simple reference compounds, including 2-methyl-2-pentene and 2,3-dimethylbutene, by W10O32(4-) and by classical O2(1deltag) sensitizers, such as methylene blue and ruthenium complexes. It is demonstrated that W10O32(4-) sensitized oxygenation of organic compounds occurs exclusively by a free radical pathway, which differs clearly from both Type I and Type II oxygenations. Comparison with Type II reactions shows that: (i) in spite of their weaker reactivity, singlet oxygen mediated reactions are associated with larger photo-oxygenation yields than W10O32(4-) induced processes, due to the longer lifetime of the reactive species; and (ii) reaction of alkenes with both singlet oxygen and decatungstate features charge transfer interactions, whose magnitude is larger in the case of O2(1deltag).

Alkenes↗
PubMed1997

Two-photon photodynamic therapy.

OBJECTIVE: We demonstrate the use of infrared excitation in conjunction with an efficient two-photon absorbing dye and a photosensitizer in photodynamic therapy. SUMMARY BACKGROUND DATA: An efficient two-photon absorbing dye is excited by short infrared (800 nm) laser pulses, which transfer its energy to the photosensitizer and the photosensitizer, in turn, generates the singlet oxygen. METHODS: A new approach to photodynamic cancer therapy based on the strong two-photon absorption of certain newly developed organic molecules. Near infrared pulsed laser light efficiently excites these molecules which, in turn, transfer the energy to the photosensitizer used in photodynamic therapy. RESULTS: A newly synthesized two-photon absorbing dye 4-[N-(2-hydroxyethyl)-N-(methyl) amino phenyl]-4'-(6-hydroxyhexyl sulfonyl)stilbene (APSS), which exhibits a strong two-photon absorption at 800 nm, and upconverted fluorescence at 520 nm, in solution in the presence of a photosensitizer was found to generate singlet oxygen under infrared excitation (800 nm). The generation of singlet oxygen in a reaction system containing two-photon absorbing dye and photosensitizer under infrared excitation has been chemically detected by using ADPA (9,10-anthracenedipropionic acid) as singlet oxygen detector. CONCLUSIONS: The efficient two-photon absorption of certain chromophores can be used to extend photodynamic therapy to the near infrared spectral region. Whereas the photosensitizer itself may not exhibit two-photon absorption, it could be used in conjunction with one of these new chromophores. The chromophores can act as "photon harvesters" whereby they absorb two photons of near infrared light and transfer the energy to the photosensitizer, which can generate singlet oxygen in the presence of atmospheric oxygen.

Absorption↗
PubMed1990

Spectroscopic studies of cutaneous photosensitizing agents--XV. Anthralin and its oxidation product 1,8-dihydroxyanthraquinone.

The photochemistry (Type I and II) of anthralin and its photo-oxidation product 1,8-dihydroxyanthraquinone (1,8-DHAQ) has been studied in ethanol, acetonitrile and dimethylsulfoxide using spin-trapping and direct detection of singlet oxygen (1O2) luminescence techniques. In ethanol, where it exists in its neutral form (AN), anthralin does not undergo either Type I or II reactions upon UV-irradiation. In contrast, irradiation of anthralin in acetonitrile, a solvent in which anthralin is partially converted to its corresponding mono-anion (AN-), generates both superoxide and singlet oxygen. Irradiation of anthralin in dimethylsulfoxide, where the AN- form is present in substantial quantity, generates superoxide and solvent derived radicals but no detectable singlet oxygen. UV-irradiation of 1,8-DHAQ in ethanol and acetonitrile produces both superoxide and singlet oxygen in significant yields. In dimethylsulfoxide, on the other hand, only superoxide and solvent derived radicals are observed. The 1O2 quantum yield for AN- and 1,8-DHAQ in acetonitrile were determined to be 0.14 and 0.88 relative to rose bengal in the same solvent. These findings suggest that the AN photosensitization occurs via Type I and II pathways, is solvent dependent and involves AN- as well as its oxidation product 1,8-DHAQ, which is a more potent generator of both singlet oxygen and superoxide.

Anthralin↗
PubMed2001

Chlorin-type photosensitizers photochemically derived from vinyl porphyrins.

The reaction of singlet oxygen with four vinyl-substituted dicarboxylic porphyrins, vinyldeuteroporphyrin (VD), ethylvinyldeuteroporphyrin (EVD), hydroxyethylvinyldeuteroporphyrin (HVD) and protoporphyrin (PP) in organic solutions is investigated. The main products, the "hydroxyaldehyde" chlorin-type derivatives, are formed with a concentration-dependent photochemical quantum yield that reaches a maximum of 7.4 +/- 1.6 x 10(-3). However, owing to the high turnover of singlet-oxygen production, these chlorin-type compounds are easily prepared photochemically with a chemical yield of 70% and little side product formation. In chemical ionization mass spectrometry, these compounds display an unusual fragmentation with a loss of 16 mass units. This is attributed to the loss of the oxygen bound to the saturated carbon of the modified pyrrole unit. All these compounds sensitize the formation of singlet oxygen with a yield around 0.8. They interact with singlet oxygen with rate constants of 5 x 10(6)-9 x 10(6) M-1 s-1, lower than those measured for vinyl porphyrins. These data are likely to help in the characterization of photoproducts of vinyl porphyrins relevant to photodynamic therapy (PP, HVD). As exemplified with VD and EVD, they also point out the reaction of singlet oxygen as an efficient route to chlorin-type photosensitizers.

Chromatography, High Pressure Liquid↗
PubMed2001

Girard's reagent P derivative of beta-Apo-8'-carotenal: a potent photoprotective agent.

A cationic carotenoid derivative (GRP-carotenal) was synthesized by the reaction of Girard's reagent P and beta-apo-8'-carotenal. The singlet-oxygen quenching constants for GRP-carotenal were 1.3 +/- 0.1 x 10(10) and 1.0 +/- 0.1 x 10(10) M-1 s-1 in acetonitrile and in detergent micelles, respectively. Photosensitized damage to K562 leukemia cells from cis-di(4-sulfonatophenyl)diphenylporphine, hypericin and protoporphyrin IX was inhibited by GRP-carotenal under conditions where beta-apo-8'-carotenal, beta-carotene and crocetin were ineffective. The unique cytoprotective properties of GRP-carotenal, relative to the other carotenoids studied, could not be explained by the differences in the cell content of the various carotenoids or by the changes in the cell content of the photosensitizers used. Photosensitizer fluorescence from labeled K562 cells was reduced by GRP-carotenal but not by the other carotenoids studied. The novel photoprotective properties of GRP-carotenal may be due to its subcellular distribution. In photosensitizer-containing detergent micelles, novel properties of GRP-carotenal were not apparent. None of the carotenoids studied reduced photosensitizer fluorescence or singlet-oxygen generation. Singlet-oxygen quenching by GRP-carotenal and by beta-apo-8'-carotenal were roughly the same. Crocetin has a singlet-oxygen quenching constant that is about a factor of five lower. Singlet-oxygen quenching by beta-carotene was limited by its aggregation.

Anthracenes↗
PubMed1983

[Mechanisms of the damaging effect of fluorescent dyes on the retina].

Mechanisms of the photo-damage of a fluorescent dye (methylene blue) and of the protective action of antioxidants and quenchers of singlet oxygen on the outer retinal rod segments (ORRS) and retinal function in situ and in vivo were studied. The methylene blue-induced formation of singlet oxygen in the ORRS resulted in accumulation of lipid peroxidation products, oligomerization of rhodopsin, and in a decrease in rhodopsin thermal resistance. Modification of the lipid and protein components of the visual cells by singlet oxygen inhibited the electrical activity of both isolated frog retina in situ and rabbit retina in vivo (waves a and b on the electroretinogram). The antioxidants (alpha-naphthol, alpha-tocopherol, 4-methyl-2,6-di-tert-butylphenol) and singlet oxygen quenchers, [1,4-diazabicyclo (2,2,2)octane] and alpha-tocopherol prevented the damaging effects of the fluorescent dye induced by singlet oxygen formation.

Animals↗
PubMed2001

A computational study of ethylene C-H bond activation by.

It has previously been demonstrated that both [(C5Me5)Ir(PMe3)(CH=CH2)H] and [(C5Me5)Ir(PMe3)(H2C=CH2)] are formed when [(C5Me5)Ir(PMe3)] is thermolytically generated in the presence of ethylene. At higher temperatures, the vinyl hydride is converted to the eta2-ethylene adduct. Density functional theory has now been used to investigate this reaction, using the B3LYP functional, two types of basis sets (LanL2DZ and TZV*), and two models of the [(C5R5)Ir(PR3)] species (R=H and CH3). The study consists of full optimizations of local minima, first-order saddle points, and minimum energy crossing points (MECP). The experimental results are best accounted for by considering both singlet and triplet spin surfaces. The relative energies of singlet [(C5R5)Ir(PR3)(CH3)H], [(C5R5)Ir(PR3)(CH=CH2)H], and [(C5R5)Ir(PR3)(H2C=CH2)] are in good agreement with experiment, as is the calculated barrier for the conversion from the vinyl hydride to the eta2-alkene complex. However, the singlet surface alone fails to explain the experimentally observed product ratio, or the intermediate inferred from experimental isotope effect studies. Locating the MECP between singlet and triplet surfaces indicates that the thermolysis of the singlet alkyl hydride precursor directly forms triplet [(C5R5)Ir(PR3)]. The weak vanderWaals adduct of triplet [(C5R5)Ir(PR3)] and ethylene is proposed to be the key intermediate in the overall reaction. The interchanging of the available ethylene C-H bonds in this triplet sigma complex accounts for the observed kinetic isotope effects, and partitioning between alkene pi-complexation and C-H bond activation may also occur from this common intermediate. The possible role of steric factors and molecular dynamics are also discussed.

Journal Article↗
PubMedDate not supplied

Light-harvesting function of carotenoids in photo-synthesis: the roles of the newly found 1(1)Bu- state.

This minireview article highlights the energetics and the dynamics of the 1(1)B(u)(-) and 3(1)A(g)(-) states of carotenoids discovered very recently. Those "hidden" covalent states have been revealed by measurements of resonance-Raman excitation profiles of crystalline carotenoids. The dependence of the energies of the low-lying singlet states, including the 1(1)B(u)(+), 3(1)A(g)(-), 1(1)B(u)(-), and 2(1)A(g)(-) states, on the number of conjugated double bonds (n) is in agreement with the extrapolation of those state energies calculated by Tavan and Schulten for shorter polyenes (P. Tavan and K. Schulten, Journal of Chemical Physics, 1986, vol. 85, pp. 6602-6609). It has also been shown that the internal-conversion processes among those singlet states take place in accord with the state ordering, i.e., 1(1)B(u)(+) --> 1(1)B(u)(-) --> 2(1)A(g)(-) --> 1(1)A(g)(-) (the ground state) for carotenoids having n = 9 and 10, whereas 1(1)B(u)(+) --> 3(1)A(g)(-) --> 1(1)B(u) (-) --> 2(1)A(g)(-) --> 1(1)A(g)(-) for carotenoids having n = 11-13. Radiative transitions of 1(1)B(u)(+) --> 2(1)A(g)(-) and 1(1)B(u)(-) --> 2(1)A(g)(-) as well as a branching into the triplet manifold of 1(1)B(u)(-) --> 1(3)A(g) --> 1(3)B(u) have also been found. Those low-lying singlet states of all-trans carotenoids can facilitate multiple channels of singlet-energy transfer to bacteriochlorophyll in the LH2 antenna complexes of purple photosynthetic bacteria. Thus, the newly found 1(1)B(u)(-) and 3(1)A(g)(-) states of carotenoids need to be incorporated into the picture of carotenoid-to-bacteriochlorophyll singlet-energy transfer.

Bacteriochlorophylls↗
PubMed2005

Artificial photosynthetic reaction centers: mimicking sequential electron and triplet-energy transfer.

An artificial photosynthetic reaction center consisting of a carotenoid (C), a dimesitylporphyrin (P), and a bis(heptafluoropropyl)porphyrin (P(F)), C-P-P(F) , and the related triad in which the central porphyrin has been metalated to give C-P(Zn)-P(F) have been synthesized and characterized by transient spectroscopy. These triads are models for amphipathic triads having a carboxylate group attached to the P(F) moiety; they are designed to carry out redox processes across lipid bilayers. Triad C-P-P(F) undergoes rapid singlet-singlet energy transfer between the porphyrin moieties, so that their excited states are in equilibrium. In benzonitrile, photoinduced electron transfer from the first excited singlet state of P and hole transfer from the first excited singlet state of P(F) yield the initial charge-separated state C-P(.) (+)-P(F) (.) (-). Subsequent hole transfer to the carotenoid moiety generates the final charge-separated state C(.) (+)-P-P(F) (.) (-), which has a lifetime of 1.1 mus and is formed with a quantum yield of 0.24. In triad C-P(Zn)-P(F) energy transfer from the P(Zn) excited singlet to the P(F) moiety yields C-P(Zn)-(1)P(F) . A series of electron-transfer reactions analogous to those observed in C-P-P(F) generates C(.) (+)-P(Zn)-P(F) (.) (-), which has a lifetime of 750 ns and is formed with a quantum yield of 0.25. Flash photolysis experiments in liposomes containing an amphipathic version of C-P(Zn)-P(F) demonstrate that the added driving force for photoinduced electron transfer in the metalated triad is useful for promoting electron transfer in the low-dielectric environment of artificial biological membranes. In argon-saturated toluene solutions of C-P-P(F) and C-P(Zn)-P(F) , charge separation is not observed and a considerable yield of triplet species is generated upon excitation of the porphyrin moieties. In both triads triplet energy localized in the P(F) moiety is channeled to the carotenoid chromophore by a triplet energy-transfer relay mechanism. Certain photophysical characteristics of these triads, including the sequential electron transfer and the triplet energy-transfer relay mechanism, are reminiscent of those observed in natural reaction centers of photosynthetic bacteria.

Carotenoids↗
PubMed1998

UVA irradiation of human lens proteins produces residual oxidation of ascorbic acid even in the presence of high levels of glutathione.

The oxidation products of ascorbic acid (AscH-) can rapidly glycate and crosslink lens proteins in vitro, producing fluorophores and browning products similar to those present in cataractous lenses. The accumulation of AscH- oxidation products, however, would largely be prevented by the millimolar levels of glutathione (GSH) present in human lens. Here we investigate whether protein aggregation could allow the oxidation of AscH- by UVA-induced reactive oxygen species in the presence of physiological levels of GSH. The metal-catalyzed oxidation of 1.0 mM AscH- by 50 microM Cu(II) was almost complete after 1 h, but no oxidation was seen in the presence of GSH concentrations as low as 0.5 mM. UVA irradiation of protein aggregates from human lens, which accumulated more than 2.0 mM singlet oxygen after 1 h, caused a 50-60% oxidation of 1.0 mM AscH-. The addition of 204 mM GSH, however, decreased AscH- oxidation by less than half, and 30% of the AscH- was oxidized even in the presence of 15 mM GSH. This diminished protection may be due, in part, to the ability of AscH-, but not GSH, to penetrate to the sites of singlet oxygen generation located within the protein. Consistent with this hypothesis, greater GSH protection was seen when a proteolytic digest of the human proteins was subjected to the same irradiation or when singlet oxygen was chemically generated from 3-(4-methyl-1-naphthyl)propionic acid endoperoxide (MNPAE) at 37 degrees C in the medium. The addition of 50 microM Cu(II) had no effect on the rate of degradation of dehydroascorbic acid (DHA). Singlet oxygen, either UVA- or MNPAE-generated, increased the rate of DHA loss. This secondary oxidation of DHA by singlet oxygen would allow the accumulation of AscH- oxidation products was not reducible by GSH. Therefore, the data presented here argue that the protein aggregation seen in older human lenses may permit oxidized AscH--induced crosslinking to occur even at physiological GSH levels.

Aging↗
PubMed1990

Photophysical properties and photodynamic activity in vivo of some tetrapyrroles.

Some of the photophysical properties (stationary absorbance and fluorescence, fluorescence decay times and singlet oxygen quantum yields) of pheophorbide a, metal-free, ClAl-, Cu- and Mg-t-butyl-substituted phthalocyanines, metal-free, ClAl- and Cu-t-butyl-substituted naphthalocyanines and of a number of tetraphenylporphyrins (5,10,15,20-tetraphenylporphyrin, 5,10,15,20-tetra(m-hydroxyphenyl)porphyrin, 5,10,15,20-tetra(p-hydroxyphenyl)porphyrin) have been studied in comparison with hematoporphyrin IX in order to select potent photosensitizers for the photodynamic treatment of cancer. The photodynamic activity of these compounds was investigated using Lewis lung carcinoma in mice. As a consequence of the photophysical parameters (relatively short singlet state lifetimes, and high singlet oxygen quantum yields) the photodynamic activities of pheophorbide a, t-butyl-substituted ClAl-phthalocyanine and ClAl-naphthalocyanine were selected for study in greater detail. Under the conditions employed in the present study, pheophorbide a was found to be the most effective sensitizer, as judged from its strong absorption at the excitation wavelength as compared with the hematoporphyrin derivative and greater singlet oxygen quantum yield relative to the phthalocyanines and naphthalocyanines. The photodynamic activity was observed to be strongly dependent on the photophysical parameters of the compounds. The primary mechanism underlying the photodynamic activity of these sensitizers probably consists of energy transfer from the lowest triplet state of the dyes to molecular oxygen, resulting in the formation of singlet oxygen (type II of photosensitization).

Animals↗
PubMed1994

Effects of structural modifications on the photosensitizing properties of dialkylcarbocyanine dyes in homogeneous and heterogeneous solutions.

The photophysical characterization of structurally modified symmetric dialkylthiacarbocyanine dyes in homogeneous and biomimetic media is reported. The aim of the two specific structural modifications was to increase singlet oxygen production, hence enhancing the photosensitizing properties of these cyanine dyes. Specifically, (1) the sulfur was exchanged with selenium in order to enhance intersystem crossing via an internal heavy atom effect and (2) substituents of differing size were introduced into the meso-position of the polymethine chain to reduce photoisomerization. The result of incorporation of an internal heavy atom (selenium) into the structure of the dye yields the expected effect: this modification results in a 22-fold increase in the rate of intersystem crossing, but does not change the remaining competing deactivation rates of the first excited singlet state. As a consequence, singlet oxygen quantum yields increase from 0.001 to 0.014 in ethanol and from 0.006 to 0.08 in unilamellar liposomes. In the case of the meso-substituted thiacarbocyanine dyes, a significant reduction in photoisomerization is indeed observed. However, this modification drastically enhances internal conversion which then becomes the main deactivation pathway of the first excited singlet state. As a result, very small fluorescence and singlet oxygen quantum yields are obtained, e.g. 0.006 and 0.001, respectively, in ethanol.

Carbocyanines↗
PubMed1996

Energy migration in the light-harvesting antenna of the photosynthetic bacterium Rhodospirillum rubrum studied by time-resolved excitation annihilation at 77 K.

The intensity dependence of picosecond kinetics in the light-harvesting antenna of the photosynthetic bacterium Rhodospirillum rubrum is studied at 77 K. By changing either the average excitation intensity or the pulse intensity we have been able to discriminate singlet-singlet and singlet-triplet annihilation. It is shown that the kinetics of both annihilation types are well characterized by the concept of percolative excitation dynamics leading to the time-dependent annihilation rates. The time dependence of these two types of annihilation rates is qualitatively different, whereas the dependencies can be related through the same adjustable parameter-a spectral dimension of fractal-like structures. The theoretical dependencies give a good fit to the experimental kinetics if the spectral dimension is equal to 1.5 and the overall singlet-singlet annihilation rate is close to the value obtained at room temperature. The percolative transfer is a consequence of spectral inhomogeneous broadening. The effect is more pronounced at lower temperatures because of the narrowing of homogeneous spectra.

Freezing↗
PubMed2002

Investigation of photobleaching of hypocrellin B in non-polar organic solvent and in liposome suspension.

Hypocrellin B (HB) is a natural pigment with a promising application in the photodynamic therapy (PDT) for anticancer treatment. The photobleaching of HB in non-polar organic solvents and in liposomes in aqueous solution were investigated by the measurements of absorption spectra, quenching experiments and determination of photoproducts. Control experiments indicated that the sensitizer, oxygen and light were all essential for the photobleaching of HB, which suggested that it was mainly self-sensitized photooxidation. The illumination of HB with visible light in aerobic non-polar solvent generated singlet oxygen efficiently [Phi(1O(2))=0.76] which then attacked the sensitizer HB with formation of an endoperoxide product. The endoperoxide of HB was unstable at room temperature and underwent predominantly loss of singlet oxygen with regeneration of parent HB. The singlet oxygen released from the endoperoxide of HB was detected with chemical trapping experiments. When HB was embedded in EPC liposomes, no endoperoxide product and no singlet oxygen release from the photobleaching process of HB were detected. The quenching experiments indicated that the singlet oxygen mechanism (type II) played an important role in the non-polar solvent and the free radical mechanism (type I) was predominant in liposomal aqueous solution for the photobleaching of HB.

Liposomes↗
PubMed1990

Prostaglandin H synthase: spectroscopic studies of the interaction with hydroperoxides and with indomethacin.

Prostaglandin H synthase has both a heme-dependent peroxidase activity and a cyclooxygenase activity. A current hypothesis considers the cyclooxygenase reaction to be a free radical chain reaction, initiated by an interaction of the synthase peroxidase with hydroperoxides leading to the production of a tyrosyl free radical [Stubbe, J. A. (1989) Annu. Rev. Biochem. 58, 257-285]. We have examined the kinetics of radical formation with both ethyl hydroperoxide (EtOOH) and 15-hydroperoxyeicosatetraenoic acid (15-HPETE) and have analyzed the effects of indomethacin (a selective cyclooxygenase inhibitor) and tetranitromethane (TNM; a selective agent for nitration of tyrosyl residues) on the synthase. At -14 degrees C both EtOOH and 15-HPETE generated within 5 s a free radical species whose electron paramagnetic resonance spectrum was dominated by a doublet centered at g = 2.005 (splitting of approximately 16 G; overall peak-to-trough width of 35 G) that has been attributed to tyrosyl radical. The doublet subsequently gave way to a singlet with a similar peak-to-trough width; the doublet-to-singlet transition was complete in 20-60 s. The intensity of the doublet/singlet combination peaked at 0.6 spins/heme after 120 s with EtOOH and at about 0.3 spins/heme after 20 s with 15-HPETE; the radical intensity declined slowly with EtOOH but more rapidly with 15-HPETE. Reaction of the indomethacin-synthase complex with EtOOH resulted in a narrower (peak-to-trough width of 24 G) singlet free radical signal, with no evidence of an earlier doublet; the intensity of the singlet peaked at 0.45 spins/heme after about 300 s. Reaction of TNM-treated synthase with EtOOH resulted in a singlet almost identical with that seen for the indomethacin-synthase complex. Reaction of the synthase holoenzyme with TNM at pH 8.0 led to inactivation of both cyclooxygenase and peroxidase activity, with the former being lost rapidly and completely while the latter was lost slowly and to about 50%. Ibuprofen, a competitive cyclooxygenase inhibitor, slowed the rate of inactivation of the cyclooxygenase by about 20-fold. The rate of inactivation of the cyclooxygenase activity in synthase apoenzyme by TNM was also about 20-fold less than that observed with the holoenzyme. Amino acid analyses revealed that TNM-reacted holoenzyme with less than 10% residual activity contained 1.8 nitrotyrosines/subunit; apoenzyme reacted under the same conditions had greater than 80% of the original activity and contained 0.7 nitrotyrosine/subunit.(ABSTRACT TRUNCATED AT 400 WORDS)

Cyclooxygenase Inhibitors↗