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Published on: July 17, 2020
Quenching of singlet oxygen by pyocyanin and related phenazines
Krzysztof J Reszka1, Piotr J Bilski, Bradley E Britigan
1Research Service and Medical Service, VA Medical Center, Cincinnati, OH, USA. reszkakj@ucmail.uc.edu
Abstract:
Pseudomonas aeruginosa is a human pathogen, which causes infections of various organs, including lung, skin and eye, particularly in individuals who are immunocompromised. Pyocyanin (1-hydroxy-5-methylphenazine), a cytotoxic pigment secreted by the bacterium, is among the factors that contribute to virulence of this pathogen. We have previously shown that rose bengal and riboflavin photosensitize oxidation of pyocyanin to a product(s) with diminished reactivity and toxicity. Singlet oxygen was suggested as the major oxidant, based on the inhibitory effect of sodium azide. In the present study, we used the time resolved technique to investigate direct interaction of pyocyanin and related phenazines (1-hydroxyphenazine [1-OH-Phen], 1-methoxy-5-methylphenazine [1-MeO-PCN] and phenazine methosulfate [PMS]) with (1)O(2). The rate constants for the (1)O(2) quenching (physical + chemical) by pyocyanin and 1-OH-Phen in D(2)O buffer (pD approximately 7.2) have been determined to be 4.8 x 10(8) and 6.8 x 10(8) M(-1) s(-1), respectively. 1-MeO-PCN and PMS were markedly less efficient (1)O(2) quenchers. Among the phenazines studied only phenazine methosulfate photogenerated (1)O(2) (Phi((1)O(2)) = 0.56 in acetonitrile). Interaction of (1)O(2) with pyocyanin and other related phenazines produced by the bacteria may be important in determining the potential utility of photochemical/pharmacological approaches to eradicate P. aeruginosa from infected tissues.
Insights
Pyocyanin, a virulence factor from Pseudomonas aeruginosa, is oxidized by singlet oxygen. This interaction, studied using time-resolved techniques, suggests potential for photochemically targeting bacterial infections.
Area of Science:
- Photochemistry
- Microbiology
- Biochemistry
Background:
- Pseudomonas aeruginosa is a significant human pathogen causing opportunistic infections.
- Pyocyanin, a cytotoxic pigment produced by P. aeruginosa, contributes to its virulence.
- Previous studies indicated photosensitized oxidation of pyocyanin, with singlet oxygen as a likely oxidant.
Purpose of the Study:
- To investigate the direct interaction of pyocyanin and related phenazines with singlet oxygen ((1)O(2)).
- To quantify the rate constants for singlet oxygen quenching by these compounds.
- To assess the potential of phenazines to photogenerate singlet oxygen.
Main Methods:
- Utilized time-resolved spectroscopy to study the interaction of phenazines with singlet oxygen.
- Determined rate constants for singlet oxygen quenching by pyocyanin and 1-hydroxyphenazine in D(2)O buffer.
- Measured the singlet oxygen quantum yield for phenazine methosulfate in acetonitrile.
Main Results:
- Pyocyanin and 1-hydroxyphenazine are efficient singlet oxygen quenchers, with rate constants of 4.8 x 10(8) M(-1)s(-1) and 6.8 x 10(8) M(-1)s(-1), respectively.
- 1-methoxy-5-methylphenazine and phenazine methosulfate showed markedly lower singlet oxygen quenching efficiency.
- Phenazine methosulfate was found to photogenerate singlet oxygen with a quantum yield of 0.56.
Conclusions:
- The interaction of singlet oxygen with bacterial phenazines, particularly pyocyanin, is significant.
- These findings support the potential utility of photochemical approaches for eradicating P. aeruginosa.
- Further research into photodynamic therapies targeting P. aeruginosa infections is warranted.
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