Related Carbonyl Compounds Research Articles

Effect of high stearic acid containing fat on markers for in vivo lipid peroxidation

The objective of this study was to determine the effect of high stearic acid (SA) diets versus high polyunsaturated fatty acid (PUFA) diets on several measures of lipid peroxidation in vivo. Sprague–Dawley rats were fed diets that differed only in the fat source (8% by weight) for 19 weeks. High SA fats were beef tallow (BT) and cocoa butter (CB), high PUFA fats were soybean oil (SO) and menhaden oil (MO). Urine was analyzed for lipophilic aldehydes, the secondary products of lipid peroxidation, by HPLC. Decreases (P<0.05) were found for 4 nonpolar lipophilic aldehydes and related carbonyl compounds (NPC) and 4 polar lipophilic aldehydes and related carbonyl compounds (PC) when the BT-fed group was compared to the SO-fed group. Decreases were also found to be significant for total NPC (P<0.01) and total PC (P<0.05) between BT and SO-fed groups. Serum increase in resistance to oxidation (P<0.01) was found in the BT group when compared to the SO group. The differences in urine and serum measurements in the present experiment indicate lower level of lipid peroxidation in vivo due to the consumption of high SA containing BT diet compared to high PUFA containing SO diet without raising serum triglycerides and cholesterol levels significantly for the BT-fed groups.

Incorporation of the toxic aldehyde 4‐hydroxy‐2‐trans‐nonenal into food fried in thermally oxidized soybean oil

AbstractThe toxic aldehyde 4‐hydroxy‐2‐trans‐nonenal (HNE) is an oxidation product of linoleic acid and is formed during the thermal oxidation of soybean oil at frying temperature. This investigation was conducted to determine whether HNE would be incorporated into food fried in thermally oxidized soybean oil. Commercially available liquid soybean oil was heated at 185°C for 5 h prior to frying uniform pieces of potato (1×0.5×7 cm). The oil was sampled prior to and after frying and was analyzed for the presence of HNE and other polar lipophilic aldehydes and related carbonyl compounds by HPLC. The oil was also extracted from the fried potato pieces and was analyzed identically to the frying oil. HNE was found to be a major polar lipophilic compound in the thermally oxidized frying oil, as previously published by this laboratory, and in the oil extracted from the fried potato. Similar concentrations of HNE were found in the oil prior to and after frying and in the oil extracted from the fried potato (57.53±16.31, 52.40±6.10, and 59.64±11.91 mg HNE per 100 g oil, respectively). These results indicate that toxic HNE was readily incorporated into food fried in thermally oxidized oil; extensive consumption of such fried foods could be a health concern.

An accurate prediction of adiabatic excitation energies to the low-lying electronic states for acetophenone and the related carbonyl compounds

The complete active space self-consistent field method has been used to optimize planar minimum energy structures of the lowest five electronic states for benzaldehyde, acetophenone and the related aromatic ketones. The adiabatic excitation energies from the ground state to the 3 nπ ∗(T 1), 1 nπ ∗(S 1), 3ππ ∗(T 2) and 1ππ ∗(S 2) states were determined, which are in a good agreement with the experimental band origins where available. The present calculations predict that the adiabatic excitation energy to each excited electronic state investigated is nearly a constant for a wide range of aromatic carbonyl compounds.

The in vivo antioxidant activity of soybean isoflavones in human subjects

This paper presents the in vivo antioxidant activity of soy isoflavones in human subjects determined by the urinary excretion of secondary lipid peroxidation products. Ten healthy women 18-35 years of age consumed a self-selected diet and avoided legumes, whole grains, and isoflavone containing foods. A powdered soy protein isolate was added daily to their diet that provided 3 levels of isoflavones: control 0.15, low 1.01, and high 2.01 mg/kg body weight. Subjects were randomized to consume all three diets for 13 weeks each, with each subject serving as her own control. Urine samples were analyzed from 24-hr collections at the end of each diet period for lipophilic aldehydes and related carbonyl compounds by HPLC. Results show that six of the individual urinary nonpolar compounds (NPC) levels were significantly lower due to consumption of the high isoflavone diet and one was also significantly lower due to consumption of the low isoflavone diet. The total of the individually measured urinary NPC was significantly lower with consumption of both the low and high isoflavone diets when compared with the control diet.

Formation of 4‐hydroxynonenal, a toxic aldehyde, in soybean oil at frying temperature

AbstractThe formation of 4‐hydroxy‐2‐trans‐nonenal (HNE), a mutagenic and cytotoxic product of the peroxidation of linoleic acid, was monitored in soybean oil that was heated at 185°C for 2, 4, 6, 8, and 10 h. Unheated soybean oil contained no HNE and a relatively low concentration of polar lipophilic secondary oxidation products (aldehydes and related carbonyl compounds), measured as 2,4‐dinitrophenylhydrazine derivatives by HPLC. An increase in the concentration of both HNE and total lipophilic polar oxidation products was observed with increased exposure to frying temperature. A considerable concentration of HNE had already formed at 2 h and the concentration continued to increase at 4 and 6 h of heating. After 6 h the concentration of HNE decreased, possibly due to degradation of the aldehyde with further exposure to high temperature. The loss of endogenous tocopherols was also monitored in the heated oil, and the tocopherol concentration decreased as the secondary lipid oxidation products increased.

Simultaneous determination of lipophilic aldehydes by high‐performance liquid chromatography in vegetable oil

AbstractA very sensitive high‐performance liquid chromatography (HPLC) method was developed for the simultaneous separation and measurement of nonpolar and polar lipophilic secondary lipid peroxidation products in vegetable oil. Seventeen nonpolar and 13 polar lipophilic aldehydes and related carbonyl compounds, derived from thermally oxidized soybean oil as 2,4‐dinitrophenyl hydrazones, were separated simultaneously by reversed‐phase HPLC. Detection limit for the individual compounds is 1 ng. Thirteen of the nonpolar carbonyl compounds were identified as: butanal, 2‐butanone, pentanal, 2‐pentanone, hexenal, hexanal, 2,4‐heptadienal, 2‐heptenal, octanal, 2‐nonenal, 2,4‐decadienal, decanal, and undecanal. Three of the polar carbonyl compounds were identified as: 4‐hydroxy‐2‐hexenal, 4‐hydroxy‐2‐octenal, and 4‐hydroxy‐2‐nonenal. The detection of the toxic 4‐hydroxy‐2‐nonenal, a major compound, and 4‐hydroxy‐2‐hexenal, a minor compound, in heated soybean oil is of particular importance because these toxic compounds have been shown to be absorbed from the diet.

Urinary aldehydes as indicators of lipid peroxidation in vivo

The excretion of malondialdehyde (MDA), lipophilic aldehydes and related carbonyl compounds in rat and human urine was investigated. MDA was found to be excreted mainly in the form of two adducts with lysine, indicating that its predominant reaction in vivo is with the lysine residues of proteins. Adducts with the phospholipid bases serine and ethanolamine and the nucleic acid bases guanine and deoxyguanosine also were found. Except for the adduct with deoxyguanosine (dG-MDA), the excretion of these compounds increased with peroxidative stress imposed in the form of vitamin E deficiency or the administration of iron or carbon tetrachloride. Marked differences in the concentration of dG-MDA in different tissues were correlated with their content of fatty acids having three or more double bonds, the putative source of MDA. Fourteen nonpolar and eleven polar lipophilic aldehydes and other carbonyl compounds were identified as their 2,4-diphenylhydrazine derivatives in rat urine. The excretion of five nonpolar and nine polar compounds was increased under conditions of peroxidative stress. The profile of lipophilic aldehydes obtained for human urine resembled that for rat urine. Except for a reported 4-hydroxynon-2-enal conjugate with mercapturic acid, the conjugated forms of the lipophilic aldehydes excreted in urine remain unidentified. Aldehyde excretion is influenced by numerous factors that affect the formation of lipid peroxides in vivo such as energy status, physical activity and environmental temperature, as well as by wide variations in the intake of peroxides in the diet. Consequently, urinalysis for aldehydic products of lipid peroxidation is an unreliable indicator of the general state of peroxidative stress in vivo.

Vitamin E and probucol reduce urinary lipophilic aldehydes and renal enlargement in streptozotocin-induced diabetic rats.

Diabetes mellitus is characterized by complications affecting several organs, including the kidney. Lipid peroxidation increases in diabetes and has been implicated in the pathogenesis of diabetic complications. In this study, we examined the ability of two antioxidants, vitamin E and probucol, to reduce lipid peroxidation in vivo and renal hypertrophy, an early stage of diabetic nephropathy, in rats. Animals were divided into four groups: non-diabetic, diabetic, diabetic treated with vitamin E, and diabetic treated with probucol. Animals were given antioxidants by intraperitoneal injection after induction of diabetes by streptozotocin injection. After 7 wk, lipid peroxidation in vivo was measured by analyzing urinary excretion of lipophilic aldehydes and related carbonyl compounds (LACC) as 2,4-dinitrophenylhydrazones by high-performance liquid chromatography. A number of urinary lipophilic nonpolar and polar aldehydes and related carbonyl compounds were identified, almost all of which increased in diabetes. Antioxidant treatment resulted in significantly decreased excretion of urinary LACC excretion. Antioxidant treatment of diabetic rats reduced renal hypertrophy. There was a high correlation between kidney weight and urinary LACC. Since LACC are accepted markers of lipid peroxidation, these results indicate that antioxidants can reduce the elevated lipid peroxidation of diabetes and may slow the onset of diabetic nephropathy.

Response of urinary lipophilic aldehydes and related carbonyl compounds to factors that stimulate lipid peroxidation in vivo.

Peroxidation of lipids results in the formation of a number of aldehydic and other carbonyl-containing secondary degradation products. The effect of peroxidative stimuli mediated by vitamin E deficiency, a diet high in polyunsaturated fatty acids (containing cod liver oil), and carbon tetrachloride administration on urinary excretion of a number of lipophilic aldehydes and related carbonyl compounds was examined in rats. These secondary lipid peroxidation products were measured as 2,4-dinitrophenylhydrazine derivatives. All three treatments increased urinary excretion of secondary lipid peroxidation products, although the pattern of excretion of these products varied somewhat among the treatments. Significant increases were found in butanal, hexanal, octanal, butan-2-one, pentan-2-one, hex-2-enal, hepta-2,4-dienal, 4-hydroxyhex-2-enal, 4-hydroxyoct-2-enal, 4-hydroxynon-2-enal, and a number of unidentified carbonyl compounds. These results suggest that urinary excretion of these lipophilic secondary lipid peroxidation products is a useful and noninvasive marker of whole-body lipid peroxidation.

Lipophilic aldehydes and related carbonyl compounds in rat and human urine.

Rat and human urine samples were analyzed for lipophilic aldehydes and other carbonyl products of lipid peroxidation. The following compounds were identified as their 2,4-dinitrophenyl hydrazones by cochromatography with pure standards using three solvent systems: butanal, butan-2-one, pentan-2-one, hex-2-enal, hexanal, hepta-2,4-dienal, hept-2-enal, octanal, non-2-enal, deca-2,4-dienal, 4-hydroxyhex-2-enal, and 4-hydroxynon-2-enal. In general, fasted rats excreted less of these compounds than fed rats, indicating they were partially of dietary origin or that the endogenous compounds were excreted in a form not susceptible to hydrazone formation. The compounds excreted in human urine were similar to those excreted in rat urine but were present in lower concentrations. Identification of the conjugated forms of the lipophilic aldehydes and related carbonyl compounds excreted in urine may be a source of information about their reactions in vivo.

Rotational barriers of 2-acetylthiophene and related carbonyl compounds

The barrier to internal rotation in 2-acetylthiophene was calculated by molecular mechanics, semiempirical, and ab initio methods. Comparisons were also made with acetophenone and 2-acetylfuran, as well as with the corresponding aldehydes. Although the calculated barriers were considerably higher for ab initio calculations at the 6-31 + G ∗ level, but lower for AM1 than the experimental values, the results were acceptable after suitable scaling. The PM3 and SAM1 methods, however, proved inappropriate for calculations of this kind. MM3 with the Parameter Estimator generally appears to give the most reasonable results.

2p→3d Excitations in transition metal compounds. A computational investigation on Fe(CO) 5, Fe(C 5H 5) 2 and Cr(CO) 6

Ab initio calculations of the metal 2p excitation spectra of Fe(CO) 5, Fe(C 5H 5) 2 and Cr(CO) 6 are presented. The results are discussed and compared with available experimental data and previous theoretical results obtained for related carbonyl compounds. The calculated spectra show a strong sensitivity to the nature of the ligand and the bonding situation but, in the case of complexes with the same type of attached ligand, also to the molecular symmetry and the formal d count of the metal atom. The correlation between the spectral features and the theoretical attribution of the excited states is analysed by means of appropriate MO energy level diagrams indicating the potential of the technique for obtaining detailed information on the nature of the metal-ligand bond. The good agreement between the theoretical and experimental spectra strongly supports the adequacy of the relatively simple computational scheme adopted for the calculations, provided due care is paid to an accurate treatment of the strong relaxation present in such systems, allowing a precise analysis of the experimental data for moderately sized systems.

A theoretical study of the x-ray photoelectron ionization energies of related carbonyl compounds: formaldehyde, acetaldehyde, and acetone

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA theoretical study of the x-ray photoelectron ionization energies of related carbonyl compounds: formaldehyde, acetaldehyde, and acetoneA. R. Rossi and E. R. DavidsonCite this: J. Phys. Chem. 1992, 96, 26, 10682–10687Publication Date (Print):December 1, 1992Publication History Published online1 May 2002Published inissue 1 December 1992https://doi.org/10.1021/j100205a021RIGHTS & PERMISSIONSArticle Views117Altmetric-Citations19LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (797 KB) Get e-Alerts

Exploratory study of β-carotene autoxidation

The main products in the early stages of β-carotene autoxidation were epoxides, β-ionone, β-apo-13-carotenone, retinal, and related carbonyl compounds; in the final mixture short chain carbonyl compounds predominated.

ChemInform Abstract: Cross‐Conjugated and Pseudo‐Cross‐Conjugated Mesomeric Betaines. Part 1. Synthesis and Characterization.

AbstractThe betaines mentioned in the title are prepared by cyclocondensation reactions of N‐heterocycles, e.g. the pyrazole (I), the imidazole (V), or the pyridine (XI) with carbon suboxide (II), chlorocarbonyl ketenes such as (VI), or related (thio)carbonyl compounds.

DIKETONES AS PHOTOSENSITIZING AGENTS: APPLICATION TO αLAMINO ACIDS and ENZYMES

Abstract— 2,3‐Butanedione (biacetyl), phenylglyoxal, 1,2‐cyclohexanedione and similar carbonyl compounds have been used as specific arginyl probes in enzyme chemistry. Depending on irradiation conditions, these and other related carbonyl compounds may, however, cause extensive changes in the structure of an enzyme regardless of the essentiality or unessentiality of arginyl residue for enzyme activity. Particularly biacetyl and 2,3‐pentanedione are powerful and general photoinactivators of enzymes in the visible region. A striking result of this process is the virtually total, time‐dependent loss of tryptophan fluorescence of the enzyme, which is accompanied by other irreversible structural changes. Several ketones and ketone aldehydes photoinactivate enzymes in UV light as well; phenylglyoxal and 1,2‐cyclohexanedione effectively inactivated enzymes at 254 nm and in the far UV region. In most cases, these photosensitized inactivations of an enzyme can be prevented by keeping the reaction mixture in anoxic conditions or adding singlet oxygen quenchers to the reaction mixture. 2‐Thiol‐L‐histidine, 3‐methyl‐L‐histidine and other imidazole derivatives are more effective protectors of enzymes against photodestruction than N3‐.

Novel free radicals formed by the amino-carbonyl reactions of sugars with amino acids, amines, and proteins.

Formation of novel free radicals in an early stage of the amino-carbonyl reactions of sugars with either amino acids,amines and some peptides were demonstrated by use of ESR spectroscopy. These radicals showed characteristic hyperfine ESR spectra and apparently differed from those observed in melanoidin. Formation of radicals of this type was faster at alkaline pH, but their signals were most stably observed in weakly acidic pH region and disappeared rapidly in other regions. The radicals developed even the mixtures were heated in open test tube but abolished rapidly by aeration. The results of reactions of various sugars or related carbonyl compounds with various amino compounds indicated that presence of sugar-like enedioi structure in the carbonyl compound and a primary amine group in the amino compound are necessary for the formation of the radical products, and that the spectral patterns were mainly influenced by the structure of amino compound, e.g. α-vs β-alanine, but not by the structure of sugar, except for three carbon aldehydes. Analyses of the hyperfine structures of ESR spectra lead to the assumption of the identity of the radical products as N,N’-disubstituted pyrazine radical derivatives. Formation of such free radicals was also investigated on some peptides and proteins.

ChemInform Abstract: NITRONES AND OXAZIRIDINES. XIII. CONVENIENT METHOD FOR THE OXIDATION OF PRIMARY‐ AND SECONDARY‐ALKYL AMINES TO CARBONYL COMPOUNDS

Primary- and secondary-alkyl amines have been converted in good yield into the related carbonyl compounds by sequential conversion into isopropylidene imines and 3,3-dimethyloxaziridines, followed by acidic hydrolysis of the latter. Intermediates need not be isolated.

Trans- to cis-Isomerisation of cinnamic acids and related carbonyl compounds

Polyphosphoric acid converts trans-cinnamic acid and trans-benzylidenacetophenone into their cis-isomers and trans,trans-5-phenylpenta-2,4-dienoic acid into the trans,trans-isomer.

Gas chromatography of homologous esters : VII. The retention behaviour of pyruvate esters and related carbonyl and carboxyl compounds

The retention behaviour of homologous pyruvate esters on a range of polysiloxane stationary phases is reported. The polysiloxane phases studied vary in character from essentially non-polar to those possessing donor and acceptor character within the concept of the Rohrschneider classification. The results are considered together with those of simple esters and ketones containing the ▪ and ▪ structures