title: Isoprenoid Alcohols are Susceptible to Oxidation with Singlet Oxygen and Hydroxyl Radicals.
abstract: Isoprenoids, as common constituents of all living cells, are exposed to oxidative agents--reactive oxygen species, for example, singlet oxygen or hydroxyl radicals. Despite this fact, products of oxidation of polyisoprenoids have never been characterized. In this study, chemical oxidation of isoprenoid alcohols (Prenol-2 and -10) was performed using singlet oxygen (generated in the presence of hydrogen peroxide/molybdate or upon photochemical reaction in the presence of porphyrin), oxygen (formed upon hydrogen peroxide dismutation) or hydroxyl radical (generated by the hydrogen peroxide/sonication, UV/titanium dioxide or UV/hydrogen peroxide) systems. The structure of the obtained products, hydroxy-, peroxy- and heterocyclic derivatives, was studied with the aid of mass spectrometry (MS) and nuclear magnetic resonance (NMR) methods. Furthermore, mass spectrometry with electrospray ionization appeared to be a useful analytical tool to detect the products of oxidation of isoprenoids (ESI-MS analysis), as well as to establish their structure on the basis of the fragmentation spectra of selected ions (ESI-MS/MS analysis). Taken together, susceptibility of polyisoprenoid alcohols to various oxidizing agents was shown for the first time.
authors.affiliation: Department of Lipid Biochemistry, Institute of Biochemistry and Biophysics, Polish Academy of Sciences (PAS), Pawinskiego 5a, 02-106, Warsaw, Poland. joannas@ibb.waw.pl.
authors.forename: Joanna
authors.initials: J
authors.lastname: Komaszylo Née Siedlecka
authors.affiliation: Laboratory of Mass Spectrometry, Institute of Organic Chemistry, Polish Academy of Sciences (PAS), Kasprzaka 44/52, 01-224, Warsaw, Poland. kaniam@icho.edu.pl.
authors.forename: Magdalena
authors.initials: M
authors.lastname: Kania
authors.affiliation: Laboratory of Mass Spectrometry, Institute of Organic Chemistry, Polish Academy of Sciences (PAS), Kasprzaka 44/52, 01-224, Warsaw, Poland.
authors.forename: Marek
authors.initials: M
authors.lastname: Masnyk
authors.affiliation: Laboratory of Mass Spectrometry, Institute of Organic Chemistry, Polish Academy of Sciences (PAS), Kasprzaka 44/52, 01-224, Warsaw, Poland.
authors.forename: Piotr
authors.initials: P
authors.lastname: Cmoch
authors.affiliation: Faculty of Chemistry, University of Warsaw, Warsaw, Poland.
authors.forename: Iwona
authors.initials: I
authors.lastname: Lozinska
authors.affiliation: Faculty of Chemistry, University of Warsaw, Warsaw, Poland.
authors.forename: Zbigniew
authors.initials: Z
authors.lastname: Czarnocki
authors.affiliation: Department of Lipid Biochemistry, Institute of Biochemistry and Biophysics, Polish Academy of Sciences (PAS), Pawinskiego 5a, 02-106, Warsaw, Poland.
authors.forename: Karolina
authors.initials: K
authors.lastname: Skorupinska-Tudek
authors.affiliation: Laboratory of Mass Spectrometry, Institute of Organic Chemistry, Polish Academy of Sciences (PAS), Kasprzaka 44/52, 01-224, Warsaw, Poland.
authors.forename: Witold
authors.initials: W
authors.lastname: Danikiewicz
authors.affiliation: Department of Lipid Biochemistry, Institute of Biochemistry and Biophysics, Polish Academy of Sciences (PAS), Pawinskiego 5a, 02-106, Warsaw, Poland.
authors.forename: Ewa
authors.initials: E
authors.lastname: Swiezewska
mesh_terms: D000438:Alcohols / Q000737:chemistry; D045782:Hemiterpenes; D006861:Hydrogen Peroxide / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D010084:Oxidation-Reduction; D017382:Reactive Oxygen Species / Q000737:chemistry; D026082:Singlet Oxygen / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D053719:Tandem Mass Spectrometry; D013729:Terpenes / Q000737:chemistry*
chemical_list: D000438:Alcohols; D045782:Hemiterpenes; D017382:Reactive Oxygen Species; D013729:Terpenes; C546578:prenol-10; D026082:Singlet Oxygen; D017665:Hydroxyl Radical; D006861:Hydrogen Peroxide
keywords: Hydrogen peroxide; Hydroxyl radical; Isoprenoid oxidation; Oxygen; Porphyrin; Singlet oxygen; Sodium molybdate; UV irradiation