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1.
THE CHROMOPHORES AS ENDOGENOUS SENSITIZERS INVOLVED IN THE PHOTOGENERATION OF SINGLET OXYGEN IN SPINACH THYLAKOIDS 总被引:1,自引:0,他引:1
Abstract— The photogeneration of singlet oxygen (1 O2 ) from thylakoids and the chromophores involved as endogenous sensitizers were investigated using chloroplasts and thylakoids isolated from spinach. The blue light-induced inhibition kinetics of photosynthetic electron transport and that of CTvCF, ATPase were also studied. The spectral dependence of the generation of 1 O2 from thylakoid membranes, measured by the imidazole plus RNO method, clearly demonstrated that the Fe-S centers play an important role in 1 O2 generation, acting as sensitizers in thylakoids. The photoinhibition of the electron transport in isolated chloroplasts was strikingly depressed by a lipid-soluble '02 quencher and enhanced by deuterium oxide substitution, indicating that the inhibition processes are mainly mediated by 1 O2 which is produced via photodynamic activation. The involvement of chloroplast cytochromes in the production of 1 O2 was deduced from the action spectrum for the photodynamic inhibition of the electron carrier chain. The results obtained from the kinetic studies appear consistent with the involvement of some components such as the Fe-S centers and cytochrome chromophores of the carrier chain in the generation of 1 O2 . 相似文献
2.
Chang Sook Kim Gwang Hyun Han Jin Man Kim Jin Jung 《Photochemistry and photobiology》1993,57(S1):1069-1074
Abstract— A comparative study was carried out on the in situ susceptibilities to photoinactivation of the photosystem I (PS I) and II (PS II) complexes of spinach thylakoids treated with efficient type II sensitizers. While the presence of the exogenous sensitizers caused a substantial increase in the extent of photoinactivation of whole chain electron transport, it did not affect PS I activity of thylakoids in light but exerted an enhanced photoinactivating effect only on PS II. The measurements of the action spectrum for the inhibition of PS II activity of the sensitizer-incorporated thylakoids and that for the generation of singlet oxygen (1 O2 ) from them revealed that photosensitized inactivation of PS II is directly related to the photoproduction of 1 O2 in thylakoid membranes. The results obtained in the present work clearly demonstrate an exceptional sensitivity of PS II to 1 O2 , providing circumstantial evidence that high light-induced damage to PS II may result from photosensitization reactions mediated by 1 O2 , which is not necessarily produced within the PS II complex. 相似文献
3.
Abstract— The action spectrum for the generation of singlet oxygen (1 O2 ) from mitochondrial membranes under aerobic conditions was measured at wavelengths between 360 and 600 nm, using sub-mitochondrial particles (SMP) prepared from soybean hypocotyls. The spectrum, showing a peak at about 420 nm, remarkably resembles the absorption spectra of the Fe-S centers of nonheme iron proteins. Disruption of the Fe-S centers by treating SMP with mersalyl acid resulted in a substantial decrease in the efficiency of 1 O2 generation, leaving an action spectrum whose pattern is significantly similar to the absorption spectrum of flavins, at least in the region of near UV and blue light wavelengths. Estimating the contribution of the Fe-S centers to the generation of 1 O2 from SMP, we suggest that the Fe-S centers act as very important endogenous photosensitizers in plant cells, in so far as the type II mechanism is concerned. Possible involvement of mitochondrial flavoproteins in the generation of 1 O2 is also discussed. 相似文献
4.
Abstract— In experiments on the interception of reactive intermediates of strongly oxidizing character in dye (S) sensitized photooxidations using p -nitrosodimethylaniline (RNO) as a selective scavenger, it has been observed that some substrates (A) or 1 O2 acceptors (like imidazole derivatives) induce the bleaching of RNO as followed spectrophotometrically at 440 nm. Since singlet oxygen (1 O2 ) does not react chemically with RNO, this bleaching is a consequence of 1 O2 capture by the imidazole ring which results in the formation of a trans-annular peroxide intermediate [1 O2 ] capable of inducing the bleaching of RNO (-RNO). In the absence of RNO, [1 O2 ] decomposes or rearranges into the final oxygenation product 1 O2 : 1 Δg Thus, the system imidazole plus RNO can be used as a sensitive and selective test for the presence of 1 O2 in aqueous solutions. The method can also be applied in the presence of sensitizing dyes which, under visible irradiation, can partially bleach RNO even in the absence of imidazole derivatives. In such a case, the bleaching of RNO is strongly increased by the presence of imidazoles with a characteristic dependence on their concentration. The separation of the product of RNO bleaching by thin layer chromatography can serve as additional proof of the presence of 1 O2 in the system. The imidazole plus RNO method has been applied to a number of sensitizing and non-sensitizing dyes. 相似文献
5.
Abstract— In view of the increasing attention to 1 O2 (1 Δg ) participation in the photodynamic action, different types of genetic changes in Saccharomyces cerevisiae by acridine orange sensitization were compared with respect to the response to N3 - , a well known quencher of 1 O2 . The induction of mitotic crossing over with respect to ade 2 locus and mitotic gene conversion at trp 5 locus were suppressed by the addition of N3 - suggesting the involvement of 1 O2 as a major intermediate. However, the induction of reverse mutation at ilv 1 was only slightly suppressed. These results may indicate that there are two types of photodynamic DNA damage; one is produced via 1 O2 and the other via non-1 O2 reaction pathway which lead to mitotic gene conversion and mitotic crossing over, and to mutation, respectively. 相似文献
6.
Abstract— Exploratory experiments using simulated conditions indicate that the terpene, (+)-limonene can serve to detect O2 (1 Δg ) in polluted atmospheres. 1 O2 attack on limonene results in the formation of specific oxidation products in a specific distribution; quantitative identification of these products is a highly specific test for 1 O2 . 相似文献
7.
Abstract —In vivo participation of singlet excited oxygen (1 O2 , 1 Δ9) in the photodynamic inactivation and induction of genetic changes (gene conversion) in acridine orange-sensitized yeast cells was investigated by using N3 - , an efficient 1 O2 quencher, and D2 O, a known agent for the enhancement of the lifetime of 1 O2 . The addition of N3 - protected the cells from both photodynamic actions. From an analysis of the concentration-dependent protection, about 80% of the induction of the genetic change is explainable on the basis of 1 O2 mechanism. The quantitative estimation of the N3 - protection in the inactivation was not possible because of the sigmoidal nature of the inactivation curve. The replacement of H2 O with D2 O during illumination was effective in enhancing the photodynamic inactivation but almost completely ineffective for the gene conversion induction. The deuterium effect with the cell system was clearly not as large as would be expected from in vitro experiments. This, however, could be explained from the kinetic consideration that natural quenchers of l O2 in the cell would mask the deuterium effect. By experiments with different cell stages it was demonstrated that these two modifying effects were dependent on the intracellular reaction environment. The conclusion is that 1 O2 must be the major intermediate responsible for the photodynamic actions in acridine orangesensitized yeast cells. 相似文献
8.
M. Delmelle 《Photochemistry and photobiology》1978,27(6):731-734
Abstract— All -trans retinal is dissolved in alcohols and illuminated at 365 nm in the presence of a singlet oxygen acceptor, 2,5-dimethylfuran. Illumination produces the photosensitized oxidation of the acceptor which is measured by the disappearance of its 215 nm absorption band. A kinetic study is carried out and βDMF is 1.6 × 10- -4 M . The quantum yield of 1 O2 production from the light-excited retinal is estimated to 0.096. The retinal sensitized photooxidation of dimethylfuran is inhibited by a 1 O2 quencher, 1,4-diazabicyclo(2,2,2)-octane, and enhanced by deuteration of the solvent. Deuterated solvents are known to increase 1 O2 lifetime.
The production of1 O2 from retinal is briefly discussed in relation to the damage which may be induced by light in the visual cells. 相似文献
The production of
9.
Abstract— The possibility of 1 O2 (1 Δg ) participation in the oxidation of polyphenols and quinones has been investigated in two systems: (1) the system involving autooxidation leading to oxidative polymerization and destruction, and (2) the modified Trautz-Schorigin reaction, i.e. oxidation of polyphenols and HCHO with H2 O2 in concentrated alkaline solutions. The red band with maximum at 635 nm observed in chemiluminescence of pyrocatechol, adrenaline, pyrogallol, gallic acid, adrenochrome and p -benzoquinone corresponds to the transition 2O2 (1 Δg ) → 2O2 (3 Σ- g ). Emission bands in the range 475–540 nm arise from the superposition of the 2O2 (1 Δg ) → 2O2 (3 Σ- g ) transition and radiative deactivation of excited oxidation products. In system (2) chemiluminescence has a broad band from 580 nm beyond 800 nm and much higher intensity than in system (1). Formaldehyde was found to enhance light emission in system (1) by a factor of about 30. The influence of solvents, including D2 O in which 1 O2 has varying lifetimes, on kinetics of chemiluminescence as well as quenching effect of β-carotene, hydroquinone, cysteine, bilirubin and biliverdin strongly support the involvement of 1 O2 in the chemiluminescence of both systems. 相似文献
10.
STEADY-STATE NEAR-INFRARED DETECTION OF SINGLET MOLECULAR OXYGEN: A STERN-VOLMER QUENCHING EXPERIMENT WITH SODIUM AZIDE 总被引:2,自引:1,他引:2
Abstract— A sensitive near-infrared detection system incorporating improvements to existing methodologies has been used to characterize the sodium azide quenching of the steady-state luminescence of singlet molecular oxygen at 1270 nm. Stern-Volmer plots which were linear up to 80% quenching of the 1 O2 generated by rose bengal and eosin Y yielded a rate constant of 5.8 ± 0.1 times 108 M −1 s−1 for the quenching of 1 O2 in water, while the rate constants obtained in deuterium oxide with the same sensitizers were 6.28 times 108 M −1 s−1 and 6.91 times 108 M −1 s−1 respectively. A flow system minimized the effects of photobleaching of the rose bengal. With a mercury arc light source, the instrument can be used in photosensitization experiments to detect low levels of 1 O2 production in aqueous media. 相似文献
11.
Oxidation of several lignin model compounds with alkylated paraphenolic groups by photosensitizing riboflavin (RF). rose bengal (RB) and methylene blue (MB) was examined. Photosensitizing RF cleaved l–(3'-4'-diethoxyphenyl)-1.3 dihydroxy-2-(4-methoxyphenyl)propane (I). 4-ethoxy-3-methoxyphenylglycerol-(3-guaiacyl ether (II) and l-(4'-ethoxy-3'-methoxyphenyI)-1,3 dihydroxypropane (IV) at their respective Cα -Cβ bonds. Riboflavin also oxidized 3.4-diethoxy-benzaldehyde (VI) to the corresponding acid, and hydroxylated the conjugated olefin l-(4'-ethoxy-3'-methoxyphenyl)1.2 propene (III) to yield the initial product IV. In contrast, MB and RB hydroxylated III but had no effect on I, II, IV or VI under identical conditions. This suggested RF effected transformations via a hydrogen radical abstraction (Type I) rather than a 1 O2 mediated reaction.
To confirm this, the effects of deuterium oxide (D: 0) and oxygen pressure on the photosensitizing dye reactions were examined. The effect of D2 0 on tryptophan (Trp) oxidation and hydroxylation of III by MB and RB was significant, indicating involvement of 1 O2 . D2 O had no significant effect on cleavage of the diarylpropane (I) and the olefin (III) by RF, indicating these reactions did not proceed by a Type II mechanism. While O2 pressure effect on Trp oxidation by MB was insignificant, it had a large negative effect on cleavage of I by RF. These results, coupled with the relatively slow oxidation rate of Trp by RF. indicate that photosensitizing RF produces 1 O2 inefficiently and is not effecting oxidation of these lignin model compounds via a Type II mechanism. 相似文献
To confirm this, the effects of deuterium oxide (D
12.
N. J. de Mol G. M. J. Beijersbergen van Henegouwen 《Photochemistry and photobiology》1981,33(6):815-819
Abstract— The production of singlet oxygen (1 O2 ) by a series of furocoumarins with different skin sensitizing abilities has been investigated with methods already proven to be suitable to establish the ability of 8-methoxypsoralen (8-MOP) to generate 1 O2 .
The following compounds: 5-methoxypsoralen (5-MOP), psoralen, 4,5',8-trimethylpsoralen (TMP) and 5,8–dimethoxypsoralen (5,8–DMOP), are able to generate1 O2 when irradiated with long–wave ultraviolet light. With the photobiologically inactive angelicin no 1 O2 production has been found. The relative extent of 1 O2 formation has been determined for the various furocoumarins and has been compared with literature data for the skin photosensitizing effect. The observed relation between experimental data on the one side and the literature data on the other side is discussed. 相似文献
The following compounds: 5-methoxypsoralen (5-MOP), psoralen, 4,5',8-trimethylpsoralen (TMP) and 5,8–dimethoxypsoralen (5,8–DMOP), are able to generate
13.
Abstract— The use of cyclic 1,3-dienes and polycyclic aromatic hydrocarbons as xenobiotic substrates for the interception of electronically excited (singlet) molecular oxygen (1 O2 ) in biological systems is reviewed and criticized, and the possibility of utilization of reactive endogenous substrates for 1 O2 interception is considered. The common sterols, cholesterol, 5α-cholest-7-en-3β-ol, and 5α-lanost-8-en-3β-ol each give oxidation products with 1 O2 different from those with ground-state molecular oxygen that can be distinguished from one another by simple chromatographic means. 相似文献
14.
LUMIFLAVIN-SENSITIZED PHOTOOXYGENATION OF INDOLE 总被引:1,自引:0,他引:1
Abstract— The lumiflavin-sensitized photooxygenation of indole in aqueous solutions has been investigated by means of steady light photolysis and flash photolysis. The semiquinone of lumiflavin and the half-oxidized radical of indole were formed by the reaction between triplet lumiflavin and indole (3.7 times 109 M -1 s-1 ). The semiquinone anion radical of lumiflavin reacted with oxygen to form superoxide radical. The triplet state of lumiflavin also reacted with oxygen forming singlet oxygen, 1 O2 . But the reaction between 1 O2 and indole (7 times 107 M_l s_1 ; estimated from steady light photolysis using Rose Bengal as a sensitizer) was far less efficient than the reaction between indole and triplet lumiflavin. The quantum yield of the lumiflavin-sensitized photooxygenation of dilute indole via radical processes was much higher than that via 1 O2 processes, though appreciable 1 O2 was formed. 相似文献
15.
SINGLET OXYGEN FORMATION BY SENSITIZATION OF FUROCOUMARINS COMPLEXED WITH, OR BOUND COVALENTLY TO DNA 总被引:1,自引:0,他引:1
N. J. de Mol G. M. J. Beijersbergen van Henegouwen B. van Beele 《Photochemistry and photobiology》1981,34(6):661-666
Abstract— The formation of singlet molecular oxygen (1 O2 ) by sensitization of the furocoumarins 5-methoxypsoralen (5-MOP), 8-methoxypsoralen (8-MOP) and psoralen complexed with DNA was investigated. From the results it is concluded that 5-MOP complexed with native DNA is able to generate 1 O2 , even in a larger extent than 5-MOP free in solution. Also, with 8-MOP and especially with psoralen, 1 O2 formation by the complexed compound could be observed. The 1 O2 formation sensitized by covalently bound furocoumarin was demonstrated with psoralen as a model compound. 4',5'-Dihydropsoralen, a model compound for the UVA light absorbing 4',5'monoadducts of furocoumarins to DNA, is also able to generate 1 O2 . 相似文献
16.
S. R. Fahrenholtz F. H. Doleiden A. M. Trozzolo A. A. Lamola 《Photochemistry and photobiology》1974,20(6):505-509
Abstract —D-α-tocopherol was found to be an effective quencher of 1 O2 molecules ( k = 2.5 times 108 →mol-1 s-1 in pyridine) by measuring its effect on the autosensitized photooxidation of rubrene. The quenching process was shown to be almost entirely 'physical', that is, α-tocopherol deactivated about 120 1 O2 molecules before being destroyed. The results suggest that this process may be a mechanism for the protective effect of α - tocopherol in photodynamic action. 相似文献
17.
Abstract— Yeast cells are inactivated by treatment with hematoporphyrin and light. The inactivation, which is mediated by singlet oxygen (1 O2 ), is enhanced by the presence of phosphate and chloride. Neither phosphate nor chloride has any influence on the yield of 1 O2 . Possible mechanisms for the enhancement are briefly discussed. 相似文献
18.
MECHANISM OF PHOTOSENSITIZATION BY PHEOPHORBIDE a STUDIED BY PHOTOHEMOLYSIS OF ERYTHROCYTES AND ELECTRON spIN RESONANCE SPECTROSCOPY 总被引:1,自引:0,他引:1
Abstract Phcophorbide a (PPa), a causal substance of food intoxication, when excited by exposure to light wavelengths of over 600 nm, caused the photohemolysis of goat erythrocytes in proportion to the incubation time of the cells. The addition of N-3 , an effective scavenger of 1 O2 , to the medium markedly inhibited the hemolysis of erythrocytes in a concentration-dependent manner, whereas the addition of superoxide dismutase (SOD) and catalase, inhibitors of O- 2 and H2 O2 generation, respectively, to the medium had little effect on it.
Methods for converting1 O2 to a nitroxide radical by 2,2,6,6-tetramethyl-4-piperidone (TMPD) and for trapping O- 2 and OH by 5,5-dimethyl-l-pyrroline-A'-oxide (DMPO) were employed to observe directly these activated oxygens by electron spin resonance (ESR). The methods provided evidence that only 1 O2 , was produced by PPa, which was excited by light wavelengths of over 600 nm. Both the addition of N3 to the solution and the removal of oxygen from the solution inhibited the generation of 1 O2 .
These results led us to conclude that1 O2 was mainly responsible for the hemolysis of erythrocytes by photoexcited PPa. 相似文献
Methods for converting
These results led us to conclude that
19.
Abstract In the presence of the photosensitizer riboflavin at high fluence rates a photoproduct, most probably H2 O2 , is formed which causes negative phototaxis in the colorless flagellate Polytomella magna . The aim of this study was to find out whether H2 O2 is produced in a type I or II reaction. As has been shown, 1 O2 quenchers either do not influence the photodynamic action of riboflavin (furfuryl ethanol, DPBF, l -histidine, crocetin) or show slight quenching effects only at very high concentrations ≧ 10−2 M (DABCO, DMF, imidazole). D2 O is toxic to P. magna even in 1:1 and 1:2 mixtures with H2 O. On the other hand, the quenching effect of 1,4-benzoquinone, highly indicative for the type I pathway, is more than two orders of magnitude stronger than the one of the above mentioned 1 O2 quenchers. The results suggest that H2 O2 is produced in a type I reaction. Superoxide does not seem to be involved since superoxide dismutase does not diminish the photodynamic effect of riboflavin. 相似文献
20.
Abstract— The autoxidation of the catecholamine neurotoxin 6-hydroxydopamine (20 μ M ) gave rise to a chemiluminescence which was greatly stimulated by FeSO4 (20 μ M ) or by hydrogen peroxide addition (20 μ M to 2 m M ). The luminescence of both 6-hydroxydopamine alone or 6-hydroxydopamine plus hydrogen peroxide was strongly inhibited by catalase and by superoxide dismutase (both at 10 μg/m/); bovine serum albumin at 10 μg/m/ had no inhibitory effect. The luminescence was also strongly inhibited by several potent hydroxyl radical trapping agents and also by low concentrations of the 1 O2 quencher DABCO (l,4-diazabicyclo-2.2.2.-octane). Chemiluminescence was greatly enhanced in D2 O, a solvent in which 1 O2 has a prolonged lifetime. These data demonstrate the involvement of hydrogen peroxide, the superoxide radical and the hydroxyl radical in the chemiluminescence. The data are also consistent with some role for 1 O2 . 相似文献