Substrate specificity and ionization potential in chloroperoxidase- catalyzed oxidation of diesel fuel

Marcela Ayala, Norma R. Robledo, Agustin Lopez-Munguia, Rafael Vazquez-Duhalt

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

Straight-run diesel fuel containing 1.6% of sulfur was enzymatically oxidized with chloroperoxidase from Caldariomyces rumago. Most organosulfides and thiophenes were transformed to form sulfoxides and sulfones. The oxidized organosulfur compounds can be effectively removed by distillation. The resulting fraction after distillation contained only 0.27% sulfur, while the untreated straight-run diesel fuel after the same distillation process still showed 1.27% sulfur. To know the chemical nature of the products, nine organosulfur compounds and 12 polycyclic aromatic compounds (PACs) were transformed by chloroperoxidase in the presence of chloride and hydrogen peroxide. Organosulfur compounds were only oxidized to form sulfoxides and sulfones, and no chlorinated derivatives were detected, except for bithiophene. In contrast, PACs were exclusively chlorinated, and no oxidized derivatives could be found. No enzymatic activity was detected on PACs with an ionization potential higher than 8.52 eV, while in the lower region it was found that the higher the ionization potential of the PAC the lower the specific activity. On the other hand, the substrate ionization potential did not seem to influence chloroperoxidase activity in the oxidation of organosulfur compounds. All organosulfur compounds tested were oxidized by chloroperoxidase. From double-substrate experiments, it appears that organosulfur compounds are oxidized by both compound I and compound X enzyme intermediates, while PACs react only with the halogenating intermediate, compound X.

Original languageEnglish
Pages (from-to)2804-2809
Number of pages6
JournalEnvironmental Science and Technology
Volume34
Issue number13
DOIs
StatePublished - 1 Jul 2000

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Chloride Peroxidase
Ionization potential
Aromatic compounds
Diesel fuels
ionization
oxidation
substrate
Oxidation
Sulfur
Distillation
Sulfoxides
Substrates
distillation
Sulfones
sulfur
Derivatives
Thiophenes
Hydrogen Peroxide
hydrogen peroxide
organosulphur compound

Cite this

Ayala, Marcela ; Robledo, Norma R. ; Lopez-Munguia, Agustin ; Vazquez-Duhalt, Rafael. / Substrate specificity and ionization potential in chloroperoxidase- catalyzed oxidation of diesel fuel. In: Environmental Science and Technology. 2000 ; Vol. 34, No. 13. pp. 2804-2809.
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abstract = "Straight-run diesel fuel containing 1.6{\%} of sulfur was enzymatically oxidized with chloroperoxidase from Caldariomyces rumago. Most organosulfides and thiophenes were transformed to form sulfoxides and sulfones. The oxidized organosulfur compounds can be effectively removed by distillation. The resulting fraction after distillation contained only 0.27{\%} sulfur, while the untreated straight-run diesel fuel after the same distillation process still showed 1.27{\%} sulfur. To know the chemical nature of the products, nine organosulfur compounds and 12 polycyclic aromatic compounds (PACs) were transformed by chloroperoxidase in the presence of chloride and hydrogen peroxide. Organosulfur compounds were only oxidized to form sulfoxides and sulfones, and no chlorinated derivatives were detected, except for bithiophene. In contrast, PACs were exclusively chlorinated, and no oxidized derivatives could be found. No enzymatic activity was detected on PACs with an ionization potential higher than 8.52 eV, while in the lower region it was found that the higher the ionization potential of the PAC the lower the specific activity. On the other hand, the substrate ionization potential did not seem to influence chloroperoxidase activity in the oxidation of organosulfur compounds. All organosulfur compounds tested were oxidized by chloroperoxidase. From double-substrate experiments, it appears that organosulfur compounds are oxidized by both compound I and compound X enzyme intermediates, while PACs react only with the halogenating intermediate, compound X.",
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Substrate specificity and ionization potential in chloroperoxidase- catalyzed oxidation of diesel fuel. / Ayala, Marcela; Robledo, Norma R.; Lopez-Munguia, Agustin; Vazquez-Duhalt, Rafael.

In: Environmental Science and Technology, Vol. 34, No. 13, 01.07.2000, p. 2804-2809.

Research output: Contribution to journalArticle

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