103560-62-9Relevant articles and documents
Characterization of 4-oxo-2-nonenal as a novel product of lipid peroxidation
Hwa Lee,Blair
, p. 698 - 702 (2000)
Fe (II)-mediated decomposition of 13-[S-(Z,E)]-9,11-hydroperoxyoctadecadienoic (hydroperoxy-linoleic) acid resulted in the formation of three α,β-unsaturated aldehydes. At low Fe (II) concentrations or at early time points after the addition of Fe(II), two major products were observed. The least polar product had chromatographic properties that were identical with those of 4-oxo-2-nonenal. Conversion of this product to its bis-oxime derivative with hydroxylamine hydrochloride resulted in two syn- and two anti-oxime isomers that had chromatographic and mass spectral properties identical with the properties of products derived from an authentic standard of 4-oxo-2-nonenal. This confirmed for the first time that 4-oxo-2-nonenal is a major product of the Fe(II)-mediated breakdown of lipid hydroperoxides. The more polar product had chromatographic properties that were similar to those of 4-hydroperoxy-2-nonenal. LC/MS analysis of its syn- and anti-oxime isomers confirmed this structural assignment. Thus, 4-hydroperoxy-2-nonenal is a previously unrecognized major product of lipid hydroperoxide decomposition. At high Fen concentrations and at longer incubation times, a third more polar product was observed with chromatographic properties that were identical to those of 4-hydroxy-2-nonenal. The syn- and anti-oxime isomers had chromatographic and mass spectral properties identical with the properties of products derived from an authentic standard of 4-hydroxy-2-nonenal. It appears that 4-hydroperoxy-2-nonenal is formed initially and that it is then converted to 4-hydroxy-2-nonenal in the presence of high Fe (II) concentrations or by extended incubations in the presence of low Fen concentrations. It is conceivable that some of the 4-hydroperoxy-2-nonenal is also converted to 4-oxo-2-nonenal. However, we cannot rule out the possibility that it is also formed by a concerted mechanism from a rearrangement product of 13-[S-(Z,E)]-9,11-hydroperoxyoctadecadienoic acid.
In vitro synthesis of 1,N6-etheno-2′-deoxyadenosine and 1,N2-etheno-2′-deoxyguanosine by 2,4-dinitrophenol and 1,3-dinitropyrene in presence of a bacterial nitroreductase
Chiron, Serge,Barbati, Stephane,De Meo, Michel,Botta, Alain
, p. 222 - 227 (2007)
The formation of covalent nitro-PAH DNA adducts and nitro-PAH mediated oxidative lesions are two possible mechanisms for the initiation of nitro-PAH carcinogenesis. Sixty-minute incubation of 1,3-dinitropyrene (100 μM) or 1,4-dinitrophenol (100 μM) with a mixture of 150 μM NADH, 0.5 units of E. coli nitroreductase, 100 μM linoleic acid, 0.5 mM ferrous iron, and 100 μM 2′-deoxyadenosine (2′-dA) or 100 μM 2′-deoxyguanosine (2′-dG) were analyzed by liquid chromatography multistage mass spectrometry. Mixtures of 1,N6-etheno-2′-deoxyadenosine (εdA) plus 4-oxo-2-nonenal (4-ONE) and 1,N2-etheno-2′- deoxyguanosine (εdG) plus 4-ONE could be detected from 2′-dA and 2′-dG, respectively. Addition of 2% propanol inhibited the formation of etheno adducts. Analyses of disappearance kinetics of dA and dG showed that dG was more rapidly eliminated than does dA (t[1/2] = 23.3 min and 98.3 min for dG and dA, respectively). Curves of formation kinetics revealed that the peak of εdG was at 55.6 min while that of εdA was at 186.9 min. These peaks represented 1.43% and 1.25% of the original dG and dA, respectively. In both cases, the peaks were followed by rapid degradations of etheno adducts. The results, obtained in this system, do not allow any extrapolation to realistic cellular responses; nevertheless, these data questioned the validity of the use of unsubstituted etheno adducts as reliable oxidative stress and nitro-PAH exposure biomarkers.
Stereoselective Synthesis of cis-2-Ene-1,4-diones via Aerobic Oxidation of Substituted Furans Catalyzed by ABNO/HNO3
Yang, Liqun,Wang, Jingyang,Wang, Yue,Li, Xiaotong,Liu, Wei,Zhang, Zhaoguo,Xie, Xiaomin
, p. 14311 - 14320 (2021/10/25)
We report a highly efficient and selective catalytic system, ABNO (9-azabicyclo-[3.3.1]nonane N-oxyl)/HNO3, for the aerobic oxidation of substituted furans to cis-2-ene-1,4-diones under mild reaction conditions using oxygen as the oxidant. The catalyst system is amenable to various substituted (mon-, di-, and tri-) furans and tolerates diverse functional groups, including cyano, nitro, naphthyl, ketone, ester, heterocycle, and even formyl groups. Based on the control and 18O-labeling experiments, the possible mechanism of the oxidation is proposed.
Synthesis of deuterium-labeled analogs of the lipid hydroperoxide-derived bifunctional electrophile 4-oxo-2(E)-nonenal
Arora, Jasbir S.,Oe, Tomoyuki,Blair, Ian A.
experimental part, p. 247 - 251 (2012/02/03)
Lipid hydroperoxides undergo homolytic decomposition into the bifunctional 4-hydroxy-2(E)-nonenal and 4-oxo-2(E)-nonenal (ONE). These bifunctional electrophiles are highly reactive and can readily modify intracellular molecules including glutathione (GSH), deoxyribonucleic acid (DNA) and proteins. Lipid hydroperoxide-derived bifunctional electrophiles are thought to contribute to the pathogenesis of a number of diseases. ONE is an α,β-unsaturated aldehyde that can react in multiple ways and with glutathione, proteins and DNA. Heavy isotope-labeled analogs of ONE are not readily available for conducting mechanistic studies or for use as internal standards in mass spectrometry (MS)-based assays. An efficient one-step cost-effective method has been developed for the preparation of C-9 deuterium-labeled ONE. In addition, a method for specific deuterium labeling of ONE at C-2, C-3 or both C-2 and C-3 has been developed. This latter method involved the selective reduction of an intermediate alkyne either by lithium aluminum hydride or lithium aluminum deuteride and quenching with water or deuterium oxide. The availability of these heavy isotope analogs will be useful as internal standards for quantitative studies employing MS and for conducting mechanistic studies of complex interactions between ONE and DNA bases as well as between ONE and proximal amino acid residues in peptides and proteins. Copyright
