title: Nitration activates tyrosine toward reaction with the hydrated electron.
abstract: 3-Nitrotyrosine has been reported as an important biomarker of oxidative stress that may play a role in a variety of diseases. In this work, transient UV-visible absorption spectra and kinetics observed during the reaction of the hydrated electron, e(aq)(-), with 3-nitrotyrosine and derivatives thereof were investigated. The absorption spectra show characteristics of aromatic nitro anion radicals. The absorptivity of radical anion product at 300 nm is estimated to be (1.0 ± 0.2) × 10(4) M(-1) cm(-1) at pH 7.3. The rate constants determined for the reaction of e(aq)(-) with 3-nitrotyrosine, N-acetyl-3-nitrotyrosine ethyl ester and glycylnitrotyrosylglycine at neutral pH (3.0 ± 0.3) × 10(10) M(-1) s(-1), (2.9 ± 0.2) × 10(10) M(-1) s(-1) and (1.9 ± 0.2) × 10(10) M(-1) s(-1), respectively, approach the diffusion-control limit and are almost two orders of magnitude higher than those for the reactions with tyrosine and tyrosine-containing peptides. The magnitude of the rate constants supports reaction of e(aq)(-) at the nitro group, and the product absorbance at 300 nm is consistent with formation of the nitro anion radical. The pH dependence of the second-order rate constant for e(aq)(-) decay (720 nm) in the presence of 3-nitrotyrosine shows a decrease with increasing pH, consistent with unfavorable electrostatic interactions. The pH dependence of the second-order rate constant for formation of radical anion (300 nm) product suggests that deprotonation of the amino group slows the rate, which indicates that deamination to form the 1-carboxy-2-(4-hydroxy-3-nitrophenyl)ethyl radical occurs. We conclude that the presence of the nitro group activates tyrosine and derivatives toward reaction with e(aq)(-) and can affect the redox chemistry of biomolecules exposed to oxidative stress.
authors.affiliation: Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China. shiwq@mail.ihep.ac.cn
authors.forename: Wei-Qun
authors.initials: WQ
authors.lastname: Shi
authors.forename: Hai-Ying
authors.initials: HY
authors.lastname: Fu
authors.forename: Patricia L
authors.initials: PL
authors.lastname: Bounds
authors.forename: Yusa
authors.initials: Y
authors.lastname: Muroya
authors.forename: Ming-Zhang
authors.initials: MZ
authors.lastname: Lin
authors.forename: Yosuke
authors.initials: Y
authors.lastname: Katsumura
authors.forename: Yu-Liang
authors.initials: YL
authors.lastname: Zhao
authors.forename: Zhi-Fang
authors.initials: ZF
authors.lastname: Chai
mesh_terms: D000042:Absorption; D004583:Electrons; D007700:Kinetics; D009842:Oligopeptides / Q000737:chemistry / Q000378:metabolism; D011675:Pulse Radiolysis; D013057:Spectrum Analysis; D014443:Tyrosine / Q000031:analogs & derivatives* / Q000378:metabolism
chemical_list: D009842:Oligopeptides; C002744:3-nitrotyrosine; D014443:Tyrosine