4-Hydroxy-2-alkenals and other products formed by water-mediated oxidative decomposition of .alpha.,.beta.-unsaturated aldehydes

Grein, Bertram.; Huffer, Manfred; Scheller, G.; Schreier, Peter

doi:10.1021/jf00036a032

Cited by 25 publications

(15 citation statements)

References 13 publications

(14 reference statements)

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“…It is of interest to note that this product was previously detected in the water-mediated oxidative decomposition of ␣,␤-unsaturated aldehydes (28).…”

Section: Discussionmentioning

confidence: 91%

4-Hydroperoxy-2-nonenal Is Not Just an Intermediate but a Reactive Molecule That Covalently Modifies Proteins to Generate Unique Intramolecular Oxidation Products

Shimozu

Hirano

Shibata

et al. 2011

Journal of Biological Chemistry

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␣,␤-Unsaturated aldehydes generated during lipid peroxidation, such as 4-oxoalkenals and 4-hydroxyalkenals, can give rise to protein degeneration in a variety of pathological states. Although the covalent modification of proteins by these end products has been well studied, the reactivity of unstable intermediates possessing a hydroperoxy group, such as 4-hydroperoxy-2-nonenal (HPNE), with protein has received little attention. We have now established a unique protein modification in which the 4-hydroperoxy group of HPNE is involved in the formation of structurally unusual lysine adducts. In addition, we showed that one of the HPNE-specific lysine adducts constitutes the epitope of a monoclonal antibody raised against the HPNEmodified protein. Upon incubation with bovine serum albumin, HPNE preferentially reacted with the lysine residues. By employing N ␣ -benzoylglycyl-lysine, we detected two major products containing one HPNE molecule per peptide. Based on the chemical and spectroscopic evidence, the products were identified to be the N ␣ -benzoylglycyl derivatives of N ⑀ -4-hydroxynonanoic acid-lysine and N ⑀ -4-hydroxy-(2Z)-nonenoyllysine, both of which are suggested to be formed through mechanisms in which the initial HPNE-lysine adducts undergo Baeyer-Villiger-like reactions proceeding through an intramolecular oxidation catalyzed by the hydroperoxy group. On the other hand, using an HPNE-modified protein as the immunogen, we raised a monoclonal antibody against the HPNE-modified protein and identified one of the HPNE-specific lysine adducts, N ⑀ -4-hydroxynonanoic acid-lysine, as an intrinsic epitope of the monoclonal antibody. Furthermore, we demonstrated that the HPNE-specific epitopes were produced not only in the oxidized low density lipoprotein in vitro but also in the atherosclerotic lesions. These results indicated that HPNE is not just an intermediate but also a reactive molecule that could covalently modify proteins in biological systems.

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“…It is of interest to note that this product was previously detected in the water-mediated oxidative decomposition of ␣,␤-unsaturated aldehydes (28).…”

Section: Discussionmentioning

confidence: 91%

4-Hydroperoxy-2-nonenal Is Not Just an Intermediate but a Reactive Molecule That Covalently Modifies Proteins to Generate Unique Intramolecular Oxidation Products

Shimozu

Hirano

Shibata

et al. 2011

Journal of Biological Chemistry

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“…The samples for NMR spectroscopy were prepared in WILMAD 528-PP 5-mm Pyrex NMR tubes, using as solvent about 0.7 mL of 99.8% C 2 HCl 3 (Dr. Glaser AG, Basel, Switzerland) from a sealed vial. The NMR spectra were acquired on a Bruker AM-360 spectrometer (Karlsruhe, Germany), equipped with a quadrinuclear 5-mm probe head, at 360.13 MHz for 1 H and at 90.56 MHz for 13 C under standard conditions. The probe temperature was 21°C for the proton spectra and slightly higher for the carbon spectra, owing to heteronuclear composite pulse decoupling.…”

Section: Methodsmentioning

confidence: 99%

“…Residual signals 6.85 (t 1:1:1, 3 J 3-H,4-H = 6.7 Hz, 3 J 3-H,2-2 H = 2.3 Hz, 0.07 H, 3-H) and 6.12 (m, 3 J 1-H,2-H = 8.0 Hz and further couplings, 0.02 H, 2-H) indicated mono-or undeuterated (E)-2-octenal as byproducts that accounted for about 9%.No evidence for the occurrence of (Z) isomer was seen in the NMR spectrum. NOEdifference experiments with unlabeled (E)-2-octenal proved the spatial vicinity of the 1-CHO and 3-CH protons, indicating the all-trans arrangement of the C=C and C=O double bonds 13. C NMR (proton decoupled) δ (ppm,…”

mentioning

confidence: 99%

Synthesis of trans‐4,5‐epoxy‐(E)‐2‐decenal and its deuterated analog used for the development of a sensitive and selective quantification method based on isotope dilution assay with negative chemical ionization

Lin

Fay

Welti

et al. 1999

Lipids

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The volatile compound trans-4,5-epoxy-(E)-2-decenal (1) was synthesized in two steps with good overall yields. The newly developed method is based on trans-epoxidation of (E)-2-octenal with alkaline hydrogen peroxide followed by a Wittig-type chain elongation with the ylide formylmethylene triphenylphosphorane. For the synthesis of [4,5-2H2]-trans-4,5-epoxy-(E)-2-decenal (d-1), [2,3-2H2]-(E)-2-octenal was prepared by reduction of 2-octyn-1-ol with lithium aluminum deuteride and subsequent oxidation of [2,3-2H2]-(E)-2-octen-1-ol with manganese oxide. Compound d1 was used as internal standard for the quantification of 1 by isotope dilution assay. Among various mass spectrometry (MS) ionization techniques tested, negative chemical ionization with ammonia as reagent gas gave best results with respect to both sensitivity and selectivity. The detection limit was found to be at about 1 pg of the analyte introduced into the gas chromatography-MS system.

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“…In order to confirm this speculation the compounds detected in the chromatograms were subjected to a renewed oxidation in their pure form by air/Cu 2 ions. The degradation of 2-trans,4-trans-2,4-decadienal, a well known fat aroma product, by air has already been investigated by Schreier et al [11] They obtained 2-octenal, hexanal (10), 4-hydroxy-2-nonenal (4-HNE; 8 in Scheme 1), and 2-pentylfuran (9). We detected the same products in the above mentioned oxidation of LDL with Cu 2 /air, 4-HNE (8) admittedly only in trace quantities.…”

Section: Identification Of Toxic 24-decadienal In Oxidized Low-densmentioning

confidence: 99%

Identification of Toxic 2,4-Decadienal in Oxidized, Low-Density Lipoprotein by Solid-Phase Microextraction

Spiteller¹,

Spiteller²

2000

Angewandte Chemie International Edition

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4-Hydroxy-2-alkenals and other products formed by water-mediated oxidative decomposition of .alpha.,.beta.-unsaturated aldehydes

Cited by 25 publications

References 13 publications

4-Hydroperoxy-2-nonenal Is Not Just an Intermediate but a Reactive Molecule That Covalently Modifies Proteins to Generate Unique Intramolecular Oxidation Products

4-Hydroperoxy-2-nonenal Is Not Just an Intermediate but a Reactive Molecule That Covalently Modifies Proteins to Generate Unique Intramolecular Oxidation Products

Synthesis of trans‐4,5‐epoxy‐(E)‐2‐decenal and its deuterated analog used for the development of a sensitive and selective quantification method based on isotope dilution assay with negative chemical ionization

Identification of Toxic 2,4-Decadienal in Oxidized, Low-Density Lipoprotein by Solid-Phase Microextraction

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