Photoinduced Generation of H2O2 and O2•- by 6-formylpterin in Aqueous Solutions

Pteridines ◽  
2006 ◽  
Vol 17 (3) ◽  
pp. 82-89 ◽  
Author(s):  
Gabriela Petroselli ◽  
Jonas Martin Bartsch ◽  
Andrés H. Thomas

Abstract 6-Formylpterin is one of the oxidized pterins that accumulate in the white skin patches of patients affected by vitiligo. Studies of photoinduced generation of hydrogen peroxide (H2O2 ) and superoxide anion radical (O2• ) by formylpterin in acidic and alkaline aqueous solutions at 350 nm and room temperature have been performed. The photochemical processes were followed by UV-V1S spectrophotometry and enzymatic methods for H2O2 and O2•- determination. When formylpterin is irradiated a red intermediate, that has been proposed to be 6-carboxy- 5,8-dihydropterin, is generated in an O2-independent process. In the presence of air that intermediate reacts with O2 to yield H2O2 and 6-carboxyptcrin. In anaerobic conditions it undergoes a thermal O2-independent reaction which leads to a non-identified product without generation of H202 . The rate constants of such a process were determined to be 0.011 min 1 and 0.044 min1 at pH 5.4 and 10.5, respectively. (O2 · ), is also generated during photooxidation of formylpterin, probably as a consequence of the electron transfer from the red intermediate to O2 . The biomedical importance of photoinduced generation of H2O2 and O2• is discussed.

Author(s):  
D. V. Belov ◽  
S. N. Belyaev ◽  
M. V. Maksimov ◽  
G. A. Gevorgyan

This paper presents an experimental study of biocorrosion of D16T and AMg6 aluminum alloys. The determining role of reactive oxygen species in aluminum biocorrosion by a consortium of molds has been shown. A model is proposed, according to which the initiators of corrosion damage to the metal surface are superoxide anion radical and hydrogen peroxide released during the life of micromycetes. It is assumed that the initiation and development of biocorrosion occurs, among other things, as a result of the process of reductive activation of oxygen and the Fenton decomposition of hydrogen peroxide. A conclusion is made about the mechanism of the occurrence of intergranular and pitting corrosion of aluminum alloys interacting with microscopic fungi.


1984 ◽  
Vol 247 (4) ◽  
pp. H631-H637 ◽  
Author(s):  
C. W. Christman ◽  
E. P. Wei ◽  
H. A. Kontos ◽  
J. T. Povlishock ◽  
E. F. Ellis

The effects of topical application of 15-hydroperoxy-eicosatetraenoic acid (15-HPETE, 200 micrograms/ml) on cerebral arterioles were studied in anesthetized cats equipped with cranial windows. 15-HPETE induced arteriolar dilation during application, sustained dilation 1 h after washout, and reduced responsiveness to the vasoconstrictive effects of hypocapnia. Electron microscopy of cerebral arterioles disclosed discrete endothelial lesions and focal morphological abnormalities of the vascular smooth muscle. Topical application of superoxide dismutase or catalase or the combination of the two inhibited the functional and morphological abnormalities induced by 15-HPETE. The results show that the vascular effects of 15-HPETE are mediated by superoxide anion radical and hydrogen peroxide or by other radicals derived from them, such as the hydroxyl radical. The results, together with earlier findings, support the view that the oxygen radicals responsible for these cerebral vascular effects are generated via the prostaglandin hydroperoxidase reaction.


2021 ◽  
Vol 12 (4) ◽  
pp. 710-717
Author(s):  
O. L. Baik ◽  
N. Y. Kyyak ◽  
O. M. Humeniuk ◽  
V. V. Humeniuk

Mosses are pioneer plants in post-technogenic areas. Therefore, the question of adaptive reactions of mosses from these habitats represents a scientific interest. The research is devoted to the study of adaptive changes in the metabolism of the dominant moss species Bryum caespiticium Hedw., collected in the devastated territories of the Novoyavorivsk State Mining and Chemical Enterprise (SMCE) “Sirka (Sulfur)” exposed to hyperthermia and insolation, which cause oxidative stress in plants. The influence of these stressors on the activity and thermal stability of antioxidant enzymes, hydrogen peroxide content, anion radical generation and accumulation of prooxidant components in moss shoots was studied. The activity and thermal stability of peroxidase and superoxide dismutase (SOD) were analysed forB. caespiticium moss from different locations of northern exposure at the sulfur mining dump No 1 in summer and autumn. We established the dependence of the activity of antioxidant enzymes of moss on the intensity of light and temperature on the experimental plots of the dump No 1. In summer, the highest activity and thermal stability rates of peroxidase and SOD were observed. Under the conditions of the experiment in shoots of В. caespiticium from the northern peak of the dump under the influence of 2 hours temperature action (+ 42 ºС) the most significant increase in peroxidase activity was found by 1.78 times and SOD by 1.89 times, as well as increase in its thermal stability by 1.35–1.42 times, respectively. The increase in peroxidase and SOD activity, as well as the increase in their thermal stability caused by hyperthermia were negated by pre-processing with a protein biosynthesis inhibitor cyclohexamide, which may indicate the participation of the protein-synthesizing system in this process. The effect of increasing the thermal stability of enzymes can be considered as a mechanism of adaptation of the protein-synthesizing system to the action of high temperatures. Increase in the activity and thermal stability of antioxidant enzymes is caused primarily by changes in the expression of stress protein genes, which control the synthesis of specific adaptogens and protectors. The obtained results indicate that the extreme conditions of the anthropogenically transformed environment contribute to the development of forms with the highest potential abilities. The mechanism of action of high temperatures is associated with the development of oxidative stress, which is manifested in the intensification of lipid peroxidation and the generation of superoxide anion radical. It was found that temperature stress and high insolation caused an increased generation of superoxide anion radical as the main inducers of protective reactions in the samples of B. caespiticium from the experimental transect of the sulfur mining heap. It is known that the synthesis of Н2О2 occurs under stress and is a signal to start a number of molecular, biochemical and physiological processes of cells, including adaptation of plants to extreme temperatures. It is shown that high temperatures initiate the generation of hydrogen peroxide. Increased reactive oxygen species (ROS) formation, including Н2О2, under the action of extreme temperatures, can cause the activation of signaling systems. Therefore, the increase in the content of Н2О2 as a signaling mediator is a component of the antioxidant protection system. It is determined that adaptive restructuring of the metabolism of the moss В. caespiticium is associated with the accumulation of signaling prooxidant components (diene and triene conjugates and dienketones). The increase in primary lipid peroxidation products, detected by us, under the action of hyperthermia may indicate the intensification of free radical oxidation under adverse climatic conditions in the area of the sulfur production dump, which leads to the intensification of lipid peroxidation processes. The accumulation of radical and molecular lipid peroxidation products are signals for the activation of protective systems, activators of gene expression and processes that lead to increased resistance of plants.


1991 ◽  
Vol 56 (3) ◽  
pp. 657-662 ◽  
Author(s):  
Pavel Stopka ◽  
Oldřich Štrouf

The superoxide anion-radicals O2·- are generated by the ultraviolet irradiation of air- or oxygen-saturated aqueous solutions of tetramethylammonium mercaptoundecahydro-closo-dodecaborate(2-) at 77 K. The superoxide anion-radicals are formed from the oxygen molecule coordinated on the mercaptoundecahydro-closo-dodecaborate dianion. In the absence of this dianion no O2·- are generated. By the irradiation in the presence of hydrogen peroxide the formation of the superoxide anion-radicals is more intensive than in the presence of oxygen only. Simultaneously with O2·- generation the corresponding thiol radicals are formed. These radicals give the disulfide compound [B12H11S]24-. A possible role of sulfur-centered radicals in the autoxidation transformations of the mercaptoundecahydro-closo-dodecaborate dianion is discussed.


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