共查询到20条相似文献,搜索用时 31 毫秒
1.
Cristina Sconfienza Albert Van de Vorst Giulio Jori † ‡ 《Photochemistry and photobiology》1980,31(4):351-357
Abstract— Oxygenated aqueous solutions (pH 10) of L-tryptophan or tryptamine containing hematopor-phyrin and/or specific quenchers of the possible reactive intermediates were irradiated with visible light in the presence and in the absence of dispersions of sodium dodecyl sulphate micelles. The rate of loss of the indole derivatives was followed over several min. In the absence of dispersed micelles, indole derivatives appeared to be photooxidized largely by a type I mechanism involving electron transfer from triplet hematoporphyrin to the indole moiety. A type II (l O2 -involving) mechanism was of minor importance. The presence of sodium dodecyl sulphate micelles, where the porphyrin was solubilized in a monomeric state, exerted only a slight influence on the competition between the two reaction pathways described above in the case of tryptophan, which was essentially all present in the aqueous phase. On the other hand, tryptamine, when dissolved within micelles, underwent photooxidative attack exclusively by 1 O2 which was generated within a micelle, diffused through the aqueous phase and penetrated into another (tryptamine-containing) micelle; the reduced efficiency of the latter photoprocess was probably a consequence of the low probability of 1 O2 penetration into charged micelles. 相似文献
2.
Abstract A continuous argon laser has been used to study the self-sensitized photooxidation of potassium rubrene-2,3,8,9-tetracarboxylate in oxygen-saturated H2 O and D2 O. An analysis of the data obtained in concentrated solutions leads to an unexpected high value of the ratio of 1 O2 lifetimes in D2 O and H2 O, T d 2 o/T h 2 o =17 ± 1. Results obtained in diluted aqueous solutions are interpreted in terms of a re-encounter of 1 O2 and ground state substrate molecules generated in the same triplet—triplet annihilation act. 相似文献
3.
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
4.
The photooxidation of N,N -diethylhydroxylamine (DEHA) by Rose Bengal (RB) has been investigated in micellar and nonmicellar aqueous solutions. We measured the quantum yield of oxygen consumption forming H2 O2 and monitored two intermediates, the superoxide and diethylnitroxide radicals. When the pH was vaned, the quantum yield of oxidation remained constant for 6 < pH < 10.5, decreased in acidic pH, and increased considerably in NaOH solution; these changes could be attributed to the protonation and dissociation processes of the >N-OH moiety of DEHA. The formation of diethylnitroxide radical was enhanced by superoxide dismutase or strong alkaline solution. Around neutral pH, the oxidation proceeded mainly via electron transfer from DEHA to the RB triplet ( k q = 107 M -1 s-1 ) with little 1 O2 participation ( kq < 105 M -1 s-1 ). However, when RB was incorporated into micelles in alkaline solution, the contribution of the singlet oxygen pathway increased at the expense of electron transfer, which was inhibited by the less polar micellar environment. Dark autoxidation of DEHA was accelerated by heavy metal impurities and increased very strongly in NaOH solution. 相似文献
5.
—Enzyme-generated triplet acetone and triplet indole-3-aldehyde transfer energy very efficiently to chloroplasts, as indicated by the intensity of the sensitized red emission that is observed. The intermediacy of excited species of oxygen (1 O2 , O2 − , HO) has been excluded. Our results open the way for investigating energy transfer in architecturally organized systems in the absence of light. 相似文献
6.
Giulio Cauzzo Ciorgio Gennari Giulio Jori† § John D. Spikes‡ 《Photochemistry and photobiology》1977,25(4):389-395
Abstract— A kinetic investigation was performed on the photooxidation of methionine sensitized by various porphyrins at different oxygen concentrations. The rate of photooxidation was found to be strongly dependent on the nature of the sensitizer. In the case of hematoporphyrin, chelation of Mg2+ and Zn2+ and especially of Cu2+ and Fe2+ caused a significant decrease of the photosensitizing efficiency. Fluorescence and/or flash photolysis studies showed that such a decrease is ascribed to an enhancement of the non-radiative decay of the first excited singlet state as well as to a reduction of the triplet lifetime. The sensitizing efficiency is also dependent on the nature of the porphyrin side chains. A reaction mechanism involving 1 O2 as the oxidizing agent is proposed. 相似文献
7.
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
8.
R. Bonneau R. Pottier O. Bagno J. Joussot-Dubien 《Photochemistry and photobiology》1975,21(3):159-163
Abstract— The production of singlet oxygen by thiazine dye photosensitization, as measured by the rate of photooxidation of tryptophan, was found to be very sensitive to changes of pH in the range 5–9. For methylene blue in aerated solutions, the production of 1 O2 * is approximately five times more efficient in basic than in acidic medium. This was shown to be related to the p K 's of the triplet dyes, by evaluating the yields of 1 O2 * from the lifetimes and the quenching rate constants for the two ionic species of sensitizer triplets measured by laser flash photolysis. Changes in the quenching rate constants of the thiazine triplet states can be correlated with the triplet energies. 相似文献
9.
Abstract— The kinetics of the triplet-triplet energy transfer of chlorophyll α (Cha) to β carotene (Car) has been investigated in Triton X100 micelles by 353 nm laser flash photolysis. This transfer consists of an intramicellar process involving pigment species located in the same micelle. A kinetic model using a bimolecular treatment leads to a rate constant of the energy transfer in the micellar phase ( k tm ≅ 6 × 108 M -1 s-1 ) lower than the previously determined values in homogeneous solvents ( k t ≅ 4.6 ≅ 109 M -l s-l ); this result shows the high microviscosity of the micellar core. In addition, the apparent bimolecular rate constant ( k t ≅ 5.0 ≅ 1010 M -l s-1 ) appears to be an order of magnitude higher than in homogeneous solvents. The lifetime of the carotene triplet state is the same in the hydrophobic core of Triton X100 micelles (τ a = 7.7 μs) as in organic solvents (hexane or carbon disulfide). The transfer yield is controlled by the distribution of chlorophyll and carotene molecules in the micelles. 相似文献
10.
Abstract— The self-sensitized photooxidation of mesodiphenylhelianthrene in various solvents has been investigated. The involvement of 1 O2 as the reactive intermediate in the formation of the endoperoxide has been demonstrated by the quenching of the photooxidation by the efficient 1 O2 -quencher β-carotene. The rate constant for the addition of 1 O2 to mesodiphenylhelianthrene has been determined to be k R ≅ 1010 M -1 s-1 , which is the highest value hitherto known in the literature. The probability factor p , which describes the concentration independent part of the overall quantum yield, has been measured to be p =0.17. 相似文献
11.
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
12.
Abstract— The photosensitized oxidation of 10–100 μ M N -acetyl-L-tryptophanamide (NATA) in neutral aqueous solution and in the presence of various dyes proceeds by a pure O2 (1 Δg )-involving mechanism. Incorporation of the tryptophyl (Trp) residue into the polypeptide chain of human serum albumin (HSA) has no influence on the mechanism and efficiency of Trp photooxidation when sensitized either by methylene blue, a non-binding dye, or by rose bengal, a dye that gives non-covalent 1: 1 complexes with HSA. This is due to the location of the Trp residue in close proximity of the protein surface and, in the case of rose bengal, to the coincidence of the photophysical properties (including the quantum yield of O2 (1 Δg ) generation) for the free and HSA-bound dye. Hematoporphyrin also binds to HSA with 1: 1 stoichiometry, although at a different site from rose bengal. Bound Hp again displays photophysical properties very similar with those of free Hp; however, the efficiency of Trp photo-oxidation in HSA is about 5-fold higher than in NATA owing to a limited rearrangement of the protein structure, induced by Hp binding, which enhances the probability of chemical quenching of O2 (1 Δg ) by the indole ring. 相似文献
13.
14.
Abstract— To investigate the existence and energy position of a photoionization threshold. tryptophan (Trp) has been photoionized in desecrated neutral aqueous or alcoholic solution under monochromatic light of variable frequency, in presence of N2 O to scavenge the photoelectron.
Present findings and some literature data converge to show the existence of a threshold for the one photon ionization process. This threshold is located at 4.5 ± 0.1 eV and 4.85 ± 0.1 cV for Trp in aqueous and ethanol solutions. respectively, which corresponds to a lowering with respect to the gas phase ionization potential of 3.4 and 3.0 eV.
The photoionization quantum yields for Trp is found about 4 times greater at 250 nm than at Λcx = 265 nm, where φe- 4M =0.080±0.025. In such spectral range. at most one photoelectron out of 4–5 escaping geminate recombination would lead to Trp photodegradation in acrated solutions.
These results also point out that the neutral radical Trp. which has been previously observed for Λcx > 275 nm, i.e. below the ionization threshold energy—would not necessarily derive from Trp + deprotonation or cation-electron dissociative recombination. Similarly, the opening of the indole ring with formylkynurenine (FK) formation which is observed under aerobic conditions and Λcx >, 280 nm would not imply an electron attachment on O2 but reactions such as Trp +3 O2 or Trp*+3 O2 or else
相似文献
Present findings and some literature data converge to show the existence of a threshold for the one photon ionization process. This threshold is located at 4.5 ± 0.1 eV and 4.85 ± 0.1 cV for Trp in aqueous and ethanol solutions. respectively, which corresponds to a lowering with respect to the gas phase ionization potential of 3.4 and 3.0 eV.
The photoionization quantum yields for Trp is found about 4 times greater at 250 nm than at Λ
These results also point out that the neutral radical Trp. which has been previously observed for Λ
相似文献
15.
Salvatore Cannistraro Albert van de Vorst Giulio Jori† 《Photochemistry and photobiology》1978,28(2):257-259
Abstract— EPR studies of the porphyrin-sensitized photooxidation of 2, 2, 6,6-tetramethyl-piperidine to the nitroxide demonstrate that all the porphyrins examined are able to generate 1 O2 , although the efficiency of the photoprocess is dependent on the nature of the side chains. Incorporation of metal ions into the porphyrin molecule depresses or even inhibits the formation of 1 O2 . Comparison of these results with previously obtained kinetic data points out that the efficiency of porphyrins as photosensitizes is controlled by the lifetime of their lowest triplet state. 相似文献
16.
Abstract— β-Carotene, at concentrations 0.1 m M , inhibits the formation of hydroperoxides and other oxidation products in a refined petroleum oil exposed to Pyrex-filtered UV. The effect appears to be due to 1 O2 quenching. A mechanism incorporating 1 O2 and radical processes is proposed as a model for environmental photooxidation of petroleum. 相似文献
17.
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
18.
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
19.
Wayne G. Wamer William C. Timmer Rong Rong Wei Sharon A. Miller Andrua Kornhauser 《Photochemistry and photobiology》1995,61(4):336-340
Abstract— Guanosine hydroxylation was used as a marker for assessing photooxidation of DNA and RNA sensitized by monofunctional and bifunctional furocoumarins. DNA or RNA, treated with sensitizer and UVA light, was enzymatically hydrolyzed, dephosphorylated and then analyzed by reversed-phase HPLC with electrochemical detection. Hydroxylated guanosine, i.e. 8-hydroxy-2'-deoxyguanosine (8-OHdG) or 8-hydroxyguanosine (8-OHG), was quantitated. 3-Carbethoxypsoralen (3-CP) was found to be an efficient photosensitizer for oxidation of guanosine in DNA, resulting in conversion of up to 0.4% of guanosine residues to 8-OHdG. In contrast, dramatically lower levels of guanosine hydroxylation were observed in 3-CP-photosensitized RNA. Psoralen was found to be a more efficient photosensitizer than angelicin in both DNA and RNA. Additional studies of oxidation of 3-CP-photosensitized DNA indicated that double-stranded DNA is 10 times more susceptible to photooxidation than single-stranded DNA, implicating 3-CP binding to DNA as an important mechanistic step in photooxidation of guanosine. The effects of D2 O and degassing with argon on photooxidation of guanosine in DNA sensitized by 3-CP were inconsistent with a mechanism involving 1 O2 . In addition, chelation of adventitious metal ions present in preparations of DNA photosensitized by 3-CP had no effect on hydroxylation of guanosine. 相似文献
20.
Abstract— A very efficient quenching of singlet oxygen (1 O2 ) by N3 - ions has been applied to the determination of rate constants of reactions of 1 O2 with various substrates (A). This determination has been made possible by choosing experimental conditions which give simple competition between N3 - and A for 1 O2 formed in the steady state irradiation of convenient sensitizing dye (S). The consumption of oxygen by the substrate, as followed with an oxygen analyzer, decreases in the presence of low concentrations of N3 - . Using neutral air saturated aqueous solutions containing the dye phenosafranine + A and varying concentrations of N3 - , the 1 O2 rate constants for reactions with biological substrates and some radiation protective agents have been determined. 相似文献