MetaboLights
An enone that is pent-1-ene substituted by an oxo group at position 3.
Identification
pent-1-en-3-one
1-penten-3-one
1-pentene-3-one
4-penten-3-one
C2H5COCH=CH2
ethyl vinyl ketone
ethylvinyl ketone
ethylvinylketone
FEMA 3382
pent-1-en-3-one
penten-3-one
pentenone
propionylethylene
vinyl ethyl ketone
Species
olea europaea
NCBI:txid4146 34020455
homo sapiens
NCBI:txid9606 24421258
NCBI:txid9606 21386183
Europe PubMed Central results
Inhalation toxicity studies of the alpha,beta-unsaturated ketones: ethyl vinyl ketone.
Author: Morgan DL, Ward SM, Wilson RE, Price HC, O'Connor RW, Seely JC, Cunningham ML.
Abstract: The National Toxicology Program is conducting a chemical class study to investigate the structure-activity relationships for the toxicity of alpha,beta-unsaturated ketones. Ethyl vinyl ketone (EVK) was selected for study because it is a representative straight-chain aliphatic alpha,beta-unsaturated ketone with extensive use and widespread exposure. Short-term inhalation studies of EVK were conducted to provide toxicity data for comparison with the related alpha,beta-unsaturated ketones 2-cyclohexene-1-one (CHX) and methyl vinyl ketone (MVK). These data will be used in designing chronic toxicity and carcinogenicity studies of these ketones. Male and female F344 rats and B6C3F1 mice were exposed to 0, 2, 4, or 8 ppm EVK 6 h/day, 5 days/wk for 13 wk. The nasal cavity was the major target organ of EVK in both rats and mice. Pathologic findings in both the olfactory and respiratory epithelium were observed. Lesions consisted primarily of olfactory epithelial necrosis, atrophy and regeneration, and/or hyperplasia and squamous metaplasia of the respiratory epithelium. Squamous metaplasia of the respiratory epithelium was present in all rats and mice exposed to 4 and 8 ppm EVK, and these lesions were more severe in rats than in mice. Few systemic effects were observed in rats and mice exposed to EVK. A transient decrease in total leukocytes due to decrements in lymphocyte and monocyte populations was present in male rats after exposure to 8 ppm for 3 and 21 days; however, this effect was not present after exposure for 13 wk. There were no chemical-related effects on micronucleus formation in mice, or on sperm motility and vaginal cytology in either species. EVK, like other alpha,beta-unsaturated ketones, is a reactive, direct-acting gaseous irritant with toxicity limited primarily to the upper respiratory tract.
Carbene metal amide photoemitters: tailoring conformationally flexible amides for full color range emissions including white-emitting OLED.
Author: Romanov AS, Jones STE, Gu Q, Conaghan PJ, Drummond BH, Feng J, Chotard F, Buizza L, Foley M, Linnolahti M, Credgington D, Bochmann M.
Abstract: Conformationally flexible "Carbene-Metal-Amide" (CMA) complexes of copper and gold have been developed based on a combination of sterically hindered cyclic (alkyl)(amino)carbene (CAAC) and 6- and 7-ring heterocyclic amide ligands. These complexes show photoemissions across the visible spectrum with PL quantum yields of up to 89% in solution and 83% in host-guest films. Single crystal X-ray diffraction and photoluminescence (PL) studies combined with DFT calculations indicate the important role of ring structure and conformational flexibility of the amide ligands. Time-resolved PL shows efficient delayed emission with sub-microsecond to microsecond excited state lifetimes at room temperature, with radiative rates exceeding 106 s-1. Yellow organic light-emitting diodes (OLEDs) based on a 7-ring gold amide were fabricated by thermal vapor deposition, while the sky-blue to warm-white mechanochromic behavior of the gold phenothiazine-5,5-dioxide complex enabled fabrication of the first CMA-based white light-emitting OLED.
DOI: 10.1039/c9sc04589a
An analysis of volatiles in the headspace of the faeces of neonates.
Author: De Lacy Costello B, Ewen R, Ewer AK, Garner CE, Probert CS, Ratcliffe NM, Smith S.
Abstract: A gas chromatography/mass spectrometry (GCMS) analysis of the headspace from the faeces of neonates was undertaken to record the volatiles associated with preterm babies on a neonatal unit. The compounds ethanol, acetone, 2-ethyl-1-hexanol, 3-methylbutanal, hexanal and 2,3-butanedione occurred with the highest frequency. The volatiles analysed were then compared to a previously published study of the volatiles from asymptomatic adult faeces. Fewer compounds were found in the neonatal faeces and virtually no sulfides were detected, in contrast to the adult samples where carbon disulfide, dimethyl disulfide and dimethyl sulfide were ubiquitous. In addition, 7 of the most abundant 15 volatile compounds were found to be aldehydes, while in contrast only 2, acetaldehyde and benzaldehyde, were present in the most abundant 15 compounds found in the headspace of adult faeces. 2-Ethyl-1-hexanol was considerably more abundant in the neonate stool compared to adult stool, and probably reflects high exposure to plastic materials containing plasticizers. The potential of disease diagnoses from the analysis of volatiles emitted from neonate faeces is discussed.
Mutagenicity and genotoxicity of ethylvinyl ketone in bacterial tests.
Author: Deininger C, Eder E, Neudecker T, Hoffman C.
Abstract: The mutagenic and genotoxic effects of ethylvinyl ketone were investigated. This alpha, beta-unsaturated carbonyl compound is widely distributed in the environment, in particular in food. Whereas ethylvinyl ketone shows only weak genotoxicity in the SOS Chromotest with Escherichia coli PQ37, it was distinctly mutagenic per se in the Salmonella preincubation assay with TA100. Using SKF 525 (an inhibitor of microsomal monooxygenase) and trichloropropene oxide (an inhibitor of epoxide hydrolase) we found indication for additional activation via epoxidation by S9 mix. The need for further investigation of the genotoxic, mutagenic and carcinogenic effects of this compound is strongly indicated.
A review of the volatiles from the healthy human body.
Author: de Lacy Costello B, Amann A, Al-Kateb H, Flynn C, Filipiak W, Khalid T, Osborne D, Ratcliffe NM.
Abstract: A compendium of all the volatile organic compounds (VOCs) emanating from the human body (the volatolome) is for the first time reported. 1840 VOCs have been assigned from breath (872), saliva (359), blood (154), milk (256), skin secretions (532) urine (279), and faeces (381) in apparently healthy individuals. Compounds were assigned CAS registry numbers and named according to a common convention where possible. The compounds have been grouped into tables according to their chemical class or functionality to permit easy comparison. Some clear differences are observed, for instance, a lack of esters in urine with a high number in faeces. Careful use of the database is needed. The numbers may not be a true reflection of the actual VOCs present from each bodily excretion. The lack of a compound could be due to the techniques used or reflect the intensity of effort e.g. there are few publications on VOCs from blood compared to a large number on VOCs in breath. The large number of volatiles reported from skin is partly due to the methodologies used, e.g. collecting excretions on glass beads and then heating to desorb VOCs. All compounds have been included as reported (unless there was a clear discrepancy between name and chemical structure), but there may be some mistaken assignations arising from the original publications, particularly for isomers. It is the authors' intention that this database will not only be a useful database of VOCs listed in the literature, but will stimulate further study of VOCs from healthy individuals. Establishing a list of volatiles emanating from healthy individuals and increased understanding of VOC metabolic pathways is an important step for differentiating between diseases using VOCs.
Characterization of a Hemoglobin Adduct from Ethyl Vinyl Ketone Detected in Human Blood Samples.
Author: Carlsson H, Motwani HV, Osterman Golkar S, Törnqvist M.
Abstract: Electrophiles have the ability to form adducts to nucleophilic sites in proteins and DNA. Internal exposure to such compounds thus constitutes a risk for toxic effects. Screening of adducts using mass spectrometric methods by adductomic approaches offers possibilities to detect unknown electrophiles present in tissues. Previously, we employed untargeted adductomics to detect 19 unknown adducts to N-terminal valine in hemoglobin (Hb) in human blood. This article describes the characterization of one of these adducts, which was identified as the adduct from ethyl vinyl ketone (EVK). The mean adduct level was 40 ± 12 pmol/g Hb in 12 human blood samples; adduct levels from acrylamide (AA) and methyl vinyl ketone (MVK) were quantified for comparison. Using l-valine p-nitroanilide (Val-pNA), introduced as a model of the N-terminal valine, the rate of formation of the EVK adduct was studied, and the rate constant determined to 200 M(-1)h(-1) at 37 °C. In blood, the reaction rate was too fast to be feasibly measured, EVK showing a half-life <1 min. Parallel experiments with AA and MVK showed that the two vinyl ketones react approximately 2 × 10(3) times faster than AA. The EVK-Hb adduct was found to be unstable, with a half-life of 7.6 h. From the mean adduct level measured in human blood, a daily dose (area under the concentration-time-curve, AUC) of 7 nMh EVK was estimated. The AUC of AA from intake via food is about 20 times higher. EVK is naturally present in a wide range of foods and is also used as a food additive. Most probably, naturally formed EVK is a major source to observed adducts. Evaluation of available toxicological data and information on occurrence of EVK indicate that further studies of EVK are motivated. This study illustrates a quantitative strategy in the initial evaluation of the significance of an adduct detected through adduct screening.
Reactivity of Biliatresone, a Natural Biliary Toxin, with Glutathione, Histamine, and Amino Acids.
Author: Koo KA, Waisbourd-Zinman O, Wells RG, Pack M, Porter JR.
Abstract: In our previous work, we identified a natural toxin, biliatresone, from Dysphania glomulifera and D. littoralis, endemic plants associated with outbreaks of biliary atresia in Australian neonatal livestock. Biliatresone is a very rare isoflavonoid with an α-methylene ketone between two phenyls, 1,2-diaryl-2-propenone, along with methylenedioxy, dimethoxyl, and hydroxyl functional groups, that causes extrahepatic biliary toxicity in zebrafish. The toxic core of biliatresone is a methylene in the α-position relative to the ketone of 1,2-diaryl-2-propenone that serves as an electrophilic Michael acceptor. The α-methylene of biliatresone spontaneously conjugated with water and methanol (MeOH), respectively, via Michael addition in a reverse phase high-performance liquid chromatography (RP-HPLC) analysis. We here report the reactivity of biliatresone toward glutathione (GSH), several amino acids, and other thiol- or imidazole-containing biomolecules. LC-MS and HPLC analysis of the conjugation reaction showed the reactivity of biliatresone to be in the order histidine > N-acetyl-d-cysteine (D-NAC) = N-acetyl-l-cysteine (L-NAC) > histamine > glutathione ≥ cysteine ≫ glycine > glutamate > phenylalanine, while serine and adenine had no reactivity due to intramolecular hydrogen bonding in the protic solvents. The reactivity of ethyl vinyl ketone (EVK, 1-penten-3-one), an example of a highly reactive α,ß-unsaturated ketone, toward GSH gave a 6.7-fold lower reaction rate constant than that of biliatresone. The reaction rate constant of synthetic 1,2-diaryl-2-propen-1-one (DP), a core structure of the toxic molecule, was 10-fold and 1.5-fold weaker in potency compared to the reaction rate constants of biliatresone and EVK, respectively. These results demostrated that the methylenedioxy, dimethoxyl, and hydroxyl functional groups of biliatresone contribute to the stronger reactivity of the Michael acceptor α-methylene ketone toward nucleophiles compared to that of DP and EVK.
Changes in the Key Odorants and Aroma Profiles of Hamlin and Valencia Orange Juices Not from Concentrate (NFC) during Chilled Storage.
Author: Sellami I, Mall V, Schieberle P.
Abstract: Application of the aroma extract dilution analysis (AEDA) on the volatiles isolated by extraction/SAFE distillation from NFC (not from concentrate) juice from Hamlin oranges revealed 51 odor-active constituents in the flavor dilution (FD) factor range of 8 to 8192 among which vanillin, wine lactone, and ( R)-linalool appeared with the highest FD factors. The AEDA applied on the volatile fraction of the same batch of juice stored at 0 °C for 10 months under aseptic conditions showed clear changes in the aroma profile as well as in the FD factors of key odorants. The reduction in the intensity of the citrus-like, pungent, green odor attributes in the aroma profile correlated with the loss of 1-penten-3-one, acetaldehyde, and ( Z)-3-hexenal and a clear decrease in hexanal, octanal, nonanal, decanal, and ( E, E)-2,4-decadienal. Quantitation done by stabile isotope dilution assays followed by a calculation of odor activity values (ratio of concentration to odor thresholds in citrate buffer) confirmed that the quick loss of 1-penten-3-one and acetaldehyde already within a few weeks and a significant reduction in nearly all aldehydes over the storage time of 10 months were responsible for the changes in the overall aroma profile of the juice. The same approach applied on Hamlin juice from the next harvest year as well as on chilled stored NFC juice from Valencia oranges confirmed the results for another harvest year and another orange variety.
New Degradation Pathways of the Key Aroma Compound 1-Penten-3-one during Storage of Not-from-Concentrate Orange Juice.
Author: Mall V, Sellami I, Schieberle P.
Abstract: 1-Penten-3-one with its fresh and pungent smell at a very low odor threshold of 0.94 μg/L water has been characterized as impact aroma compound in many foods, such as grapefruit, orange juice, black tea, olive oil, or tomatoes. While its importance to the fresh sensation of unstored not-from-concentrate (NFC) orange juice was recently confirmed by aroma recombinates, a total loss was determined already after 4 weeks in NFC orange juice stored at 0 °C. Until now, the degradation pathway of this compound has not been clarified. Systematic model studies resulted in the identification of 1-hydroxy-3-pentanone and 4-hydroxy-3,8-decanedione as degradation products as well as S-(3-oxopentyl)-l-cysteine in the presence of the amino acid. In orange juice samples, it was found that the elevated content of 1-hydroxy-3-pentanone indicates a thermal processing, while S-(3-oxopentyl)-l-cysteine showed a significant increase during cold storage. Additionally, both compounds were identified in other food samples, such as commercial orange juices, pickled olives and olive oil, fresh tomatoes and commercial tomato juice, and black tea.
Quantum mechanical study on the oxidation of ethyl vinyl ketone initiated by an OH radical.
Author: Paul S, Gour NK, Chandra Deka R.
Abstract: Oxidation of ethyl vinyl ketone (CH2CHCOCH2CH3) by an OH radical was carried out using the M06-2X/6-311++G(d,p) level of theory. For the OH-initiated oxidation of ethyl vinyl ketone (EVK), we have considered six H-atom abstractions and three addition reactions. From the energetic calculation of the species involved therein, the potential energy surface (PES) of all the reaction channels was constructed. From the energy profile, we found that the H-atom abstraction from the methylene group (-CH2-) of CH2CHCOCH2CH3 is energetically more favourable than the other H-abstraction channels. Moreover, we also observed that OH-addition to the α-carbon of the carbon-carbon double bond of the title molecule is energetically and thermodynamically more dominant than β-carbon and carbonyl carbon. The rate coefficients for all the reaction channels were calculated using the canonical transition state theory at the temperature range of 250-450 K and it reveals that among all the reaction channels, OH-addition to α-carbon is kinetically more dominant to the total rate constant. The total rate coefficient for the reaction at 298 K is found to be in good agreement with the reported experimental rate constant. Finally, we have determined the atmospheric lifetime of the title molecule.
DOI: 10.1039/c8em00365c
Silencing and stimulating the medial amygdala impairs ejaculation but not sexual incentive motivation in male rats.
Author: Huijgens PT, Heijkoop R, Snoeren EMS.
Abstract: The medial amygdala (MeA) is a sexually dimorphic brain region that integrates sensory information and hormonal signaling, and is involved in the regulation of social behaviors. Lesion studies have shown a role for the MeA in copulation, most prominently in the promotion of ejaculation. The role of the MeA in sexual motivation, but also in temporal patterning of copulation, has not been extensively studied in rats. Here, we investigated the effect of chemogenetic inhibition and stimulation of the MeA on sexual incentive motivation and copulation in sexually experienced male rats. AAV5-CaMKIIa viral vectors coding for Gi, Gq, or no DREADDs (sham) were bilaterally infused into the MeA. Rats were assessed in the sexual incentive motivation test and copulation test upon systemic clozapine N-oxide (CNO) or vehicle administration. We report that MeA stimulation and inhibition did not affect sexual incentive motivation. Moreover, both stimulation and inhibition of the MeA decreased the number of ejaculations in a 30 min copulation test and increased ejaculation latency and the number of mounts and intromissions preceding ejaculation, while leaving the temporal pattern of copulation intact. These results indicate that the MeA may be involved in the processing of sensory feedback required to reach ejaculation threshold. The convergence of the behavioral effects of stimulating as well as inhibiting the MeA may reflect opposing behavioral control of specific neuronal populations within the MeA.
Exploring the Extra-Virgin Olive Oil Volatilome by Adding Extra Dimensions to Comprehensive Two-Dimensional Gas Chromatography and Time-of-Flight Mass Spectrometry Featuring Tandem Ionization: Validation of Ripening Markers in Headspace Linearity Conditions.
Author: Stilo F, Liberto E, Reichenbach SE, Tao Q, Bicchi C, Cordero C.
Abstract: <h4>Background</h4>Comprehensive two-dimensional gas chromatography (GC×GC) combined with time-of-flight (TOF) MS is the most informative analytical approach for chemical characterization of the complex food volatilome. Key analytical features include separation power and resolution enhancement, improved sensitivity, and structured separation patterns from chemically correlated analytes.<h4>Objective</h4>In this study, we explore the complex extra-virgin olive oil volatilome by combining headspace (HS) solid-phase microextraction (SPME), applied under HS linearity conditions to GC×GC-TOF MS and featuring hard and soft ionization in tandem.<h4>Method</h4>Multiple analytical dimensions are combined in a single run and evaluated in terms of chemical dimensionality, method absolute and relative sensitivity, identification reliability provided by spectral signatures acquired at 70 and 12 eV, and dynamic and linear range of response provided by soft ionization.<h4>Results</h4>Method effectiveness is validated on a sample set of oils from Picual olives at different ripening stages. Ripening markers [3,4-diethyl-1,5-hexadiene (RS/SR), 3,4-diethyl-1,5-hexadiene (meso), (5Z)-3-ethyl-1,5-octadiene, (5E)-3-ethyl-1,5-octadiene, (E, Z)-3,7-decadiene and (E, E)-3,7-decadiene, (Z)-2-hexenal, (Z)-3-hexenal and (Z)-3-hexenal, (E)-2-pentenal, (Z)-2-pentenal, 1-pentanol, 1-penten-3-ol, 3-pentanone, and 1-penten-3-one] and quality indexes [(Z)-3-hexenal/nonanal, (Z)-3-hexenal/octane, (E)-2-pentenal/nonanal, and (E)-2-pentenal/octane] are confirmed for their validity in HS linearity conditions.<h4>Conclusions</h4>For the complex olive oil volatilome, the proposed approach offers concrete advantages for the validation of the informative role of existing analytes while suggesting new potential markers to be studied in larger sample sets.<h4>Highlights</h4>The accurate fingerprinting of volatiles by HS-SPME operating in HS linearity conditions followed by GC×GC-TOF MS featuring tandem ionization gives the opportunity to improve the quality of analytical data and reliability of results.
Se-Enrichment Pattern, Composition, and Aroma Profile of Ripe Tomatoes after Sodium Selenate Foliar Spraying Performed at Different Plant Developmental Stages.
Author: Meucci A, Shiriaev A, Rosellini I, Malorgio F, Pezzarossa B.
Abstract: Foliar spray with selenium salts can be used to fortify tomatoes, but the results vary in relation to the Se concentration and the plant developmental stage. The effects of foliar spraying with sodium selenate at concentrations of 0, 1, and 1.5 mg Se L-1 at flowering and fruit immature green stage on Se accumulation and quality traits of tomatoes at ripening were investigated. Selenium accumulated up to 0.95 µg 100 g FW-1, with no significant difference between the two concentrations used in fruit of the first truss. The treatment performed at the flowering stage resulted in a higher selenium concentration compared to the immature green treatment in the fruit of the second truss. Cu, Zn, K, and Ca content was slightly modified by Se application, with no decrease in fruit quality. When applied at the immature green stage, Se reduced the incidence of blossom-end rot. A group of volatile organic compounds (2-phenylethyl alcohol, guaiacol, (E)-2-heptenal, 1-penten-3-one and (E)-2-pentenal), positively correlated with consumer liking and flavor intensity, increased following Se treatment. These findings indicate that foliar spraying, particularly if performed at flowering stage, is an efficient method to enrich tomatoes with Se, also resulting in positive changes in fruit aroma profile.
Changes in volatile compounds of living Pacific oyster Crassostrea gigas during air-exposed storage
Author: Kawabe S, Murakami H, Usui M, Miyasaki T.
Abstract: The changes in volatile compounds of living oysters Crassostrea gigas with shells under air-exposed storage for 7 days at 5 and 20 °C were investigated using an electronic nose system and a gas chromatography–mass spectrometer (GC/MS) with headspace solid-phase microextraction (SPME). Principal component analysis of a data matrix obtained from the electronic nose response and sensory evaluation showed deterioration of oyster odor during the storage period. Headspace SPME–GC/MS analysis revealed that 1-penten-3-one decreased to undetectable levels, and volatile carboxylic acids derived from anaerobic end-products and 1-propanol increased during air-exposed storage. The detection of trimethylamine was observed only in living oysters stored at 20 °C. Amounts of 1-penten-3-ol and 1-octen-3-ol showed few changes through the storage periods. These data suggested that most of aldehydes decreased, whereas trimethylamine and volatile carboxylic acids such as propanoic acid accumulated in deteriorated living oysters stored under air-exposed conditions. Consequently, detection of trimethylamine and volatile carboxylic acids would be useful indices for suitable storage conditions of living oysters.
Sensory-directed flavor analysis of off-flavor compounds in infant formula with deeply hydrolyzed milk protein and their possible sources
Author: Yang P, Liu C, Song H, Wang L, Wang X, Hua J.
Abstract: Off-flavor compounds in IF-DHMP were identified using sensory-directed analysis. In total, 56 types of aroma-active compounds were identified in the off-flavor (OF) samples, positive control (PC) samples, and accelerated oxidation (AO) samples. The Aroma Extraction Dilution Analysis (AEDA) results showed that methional, generated via Maillard reaction, was the most important component with the highest dilution factor in OF. The results of aroma recombination, omission and spiking experiment revealed that compounds such as pentanal, methional, (E)-2-nonenal, 3-methylbutanal, (E)-2-heptenal, nonanal, (E,E)-2,4-heptadienal, 1-penten-3-one, 1-octen-3-one, and (E,E)-2,4-nonadienal were the major sources of off-flavor in OF. We observed that the off-flavor in OF samples originated due to proteolysis, Maillard reaction, or lipid oxidation during processing rather than due to lipid oxidation during storage.
The inner temperature of the olives (cv. Leccino) before processing affects the volatile profile and the composition of the oil
Author: Dourou AM, Brizzolara S, Meoni G, Tenori L, Famiani F, Luchinat C, Tonutti P.
Abstract: The effects of pre-processing decreasing temperature (19, 15 and 10 °C) of olive fruit (cv. Leccino) harvested at three developmental stages (semi-ripe, ripe, advanced ripening) have been evaluated on oil in terms of basic quality parameters, composition, organoleptic traits, and aroma profiles. A total of 40 metabolites (volatiles and non-volatiles) were identified by ¹H NMR and GC/MS analyses. Multivariate statistical analysis showed that samples obtained from ripe and advanced ripe olives cooled at 10 and 15 °C better correlated with C6 aldehydes, mainly associated with herbal/green olfactory traits. Compounds responsible for sweet/fruity traits were more abundantly present in oil extracted from 19 °C olive samples. Decreasing pulp temperature before crushing also resulted in reduced presence of 1-penten-3-ol, 1-penten-3-one, acetic acid and ethyl alcohol, associated with specific defects of the oil. Results indicate that slightly lowering fruit temperature just before crushing modulates oil composition by reducing oil off flavours while enhancing green and fresh attributes in particular when ripe olives are processed.