Atmospheric measurements of hydroperoxides and aldehydes during field campaigns : new results due to improvement of measurements techniques

NASA Astrophysics Data System (ADS)

François, S.; Sowka, I.; Poulain, L.; Monod, A.; Wortham, H.

2003-04-01

Hydroperoxides and aldehydes are considered as atmospheric reservoirs of OH, HO_2 and RO_2 radicals and can reflect the oxidizing levels of the atmosphere. They are considered as important gas phase photo-oxidants present in the atmosphere. However, the atmospheric role of these compounds can vary from one species to another, therefore it is essential to investigate their measurement and speciation in the atmosphere. Atmospheric measurements were realized during two different field campaigns in the Marseilles area (France). Hydroperoxides were trapped in aqueous phase, with a glass coil and analyzed by HPLC/fluorescence detector with post column derivatization. Aldehydes were trapped in a liquid phase containing 2-4 DNPH, with a mist chamber and analyzed by HPLC/UV. The analytical techniques provided individual separation and quantification of seven hydroperoxides (hydrogen peroxide, hydroxymethyl hydroperoxide, bis(hydroxymethyl) peroxide, 1-hydroxyethyl hydroperoxide, methyl hydroperoxide, ethyl hydroperoxide and peroxyacetic acid) and eleven volatile aldehydes (formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, butyraldehyde, benzaldehyde, glyoxal, valeraldehyde and methylglyoxal). The first field campaign was part of the ESCOMPTE project (June 4th to July 16th 2001). During this campaign five different sampling sites, at low altitudes (<= 285 m), were investigated (maritime, urban, sub-industrial, biogenic and rural sites) and atmospheric measurements were realized during photochemical air pollution events. The second field campaign was part of the BOND project (July 2nd to July 14th 2002). Atmospheric measurements of hydroperoxides were carried out on one biogenic site, at altitude 690 m. The measurement system was improved allowing online sampling and analysis. During these field campaigns collection efficiencies were better than 96% for hydroperoxides, and from 78% to 96% for aldehydes. Detection limits were between 7,3× 10-3 μg.m-3 and 2,4× 10-1 μg.m-3 with standard deviations from 4% to 22% for hydroperoxides and between 0,55 μg.m-3 and 2,5 μg.m-3 with standard deviation from 8% to 29% for aldehydes. The results show that hydroperoxide concentrations were high, when the levels of NOx were low. Aldehyde concentrations were very high during photochemical events and both primary and secondary aldehydes were identified.

Acrolein inhalation causes myocardial strain delay and decreased cardiac performance as detected by high-frequency echocardiography in mice

EPA Science Inventory

Acrolein, an unsaturated aldehyde found in air pollution, impairs Ca2+ flux and contraction in cardiomyocytes in vitro. To better define direct and delayed functional cardiac effects, we hypothesized that a single exposure to acrolein would modify myocardial strain and performanc...

Determination of patterns of biologically relevant aldehydes in exhaled breath condensate of healthy subjects by liquid chromatography/atmospheric chemical ionization tandem mass spectrometry

PubMed Central

Andreoli, Roberta; Manini, Paola; Corradi, Massimo; Mutti, Antonio; Niessen, Wilfried M. A.

2006-01-01

A method for the simultaneous determination of several classes of aldehydes in exhaled breath condensate (EBC) was developed using liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry (LC/APCI-MS/MS). EBC is a biological matrix obtained by a relatively new, simple and noninvasive technique and provides an indirect assessment of pulmonary status. The measurement of aldehydes in EBC represents a biomarker of the effect of oxidative stress caused by smoke, disease, or strong oxidants like ozone. Malondialdehyde (MDA), acrolein, α,β-unsaturated hydroxylated aldehydes [namely 4-hydroxyhexenal (4-HHE) and 4-hydroxynonenal (4-HNE)], and saturated aldehydes (n-hexanal, n-heptanal and n-nonanal) were measured in EBC after derivatization with 2,4-dinitrophenylhydrazine (DNPH). Atmospheric pressure chemical ionization of the analytes was obtained in positiveion mode for MDA, and in negativeion mode for acrolein, 4-HHE, 4-HNE, and saturated aldehydes. DNPH derivatives were separated on a C18 column using variable proportions of 20 mM aqueous acetic acid and methanol. Linearity was established over 4–5 orders of magnitude and limits of detection were in the 0.3–1.0 nM range. Intra-day and inter-day precision were in the 1.3–9.9% range for all the compounds. MDA, acrolein and n-alkanals were detectable in all EBC samples, whereas the highly reactive 4-HHE and 4-HNE were found in only a few samples. Statistically significant higher concentrations of MDA, acrolein and n-hexanal were found in EBC from smokers. PMID:12661015

Old yellow enzymes protect against acrolein toxicity in the yeast Saccharomyces cerevisiae.

PubMed

Trotter, Eleanor W; Collinson, Emma J; Dawes, Ian W; Grant, Chris M

2006-07-01

Acrolein is a ubiquitous reactive aldehyde which is formed as a product of lipid peroxidation in biological systems. In this present study, we screened the complete set of viable deletion strains in Saccharomyces cerevisiae for sensitivity to acrolein to identify cell functions involved in resistance to reactive aldehydes. We identified 128 mutants whose gene products are localized throughout the cell. Acrolein-sensitive mutants were distributed among most major biological processes but particularly affected gene expression, metabolism, and cellular signaling. Surprisingly, the screen did not identify any antioxidants or similar stress-protective molecules, indicating that acrolein toxicity may not be mediated via reactive oxygen species. Most strikingly, a mutant lacking an old yellow enzyme (OYE2) was identified as being acrolein sensitive. Old yellow enzymes are known to reduce alpha,beta-unsaturated carbonyl compounds in vitro, but their physiological roles have remained uncertain. We show that mutants lacking OYE2, but not OYE3, are sensitive to acrolein, and overexpression of both isoenzymes increases acrolein tolerance. Our data indicate that OYE2 is required for basal levels of tolerance, whereas OYE3 expression is particularly induced following acrolein stress. Despite the range of alpha,beta-unsaturated carbonyl compounds that have been identified as substrates of old yellow enzymes in vitro, we show that old yellow enzymes specifically mediate resistance to small alpha,beta-unsaturated carbonyl compounds, such as acrolein, in vivo.

In vitro effects of aldehydes present in tobacco smoke on gene expression in human lung alveolar epithelial cells.

PubMed

Cheah, Nuan P; Pennings, Jeroen L A; Vermeulen, Jolanda P; van Schooten, Frederik J; Opperhuizen, Antoon

2013-04-01

Tobacco smoke consists of thousands of harmful components. A major class of chemicals found in tobacco smoke is formed by aldehydes, in particular formaldehyde, acetaldehyde and acrolein. The present study investigates the gene expression changes in human lung alveolar epithelial cells upon exposure to formaldehyde, acrolein and acetaldehyde at sub-cytotoxic levels. We exposed A549 cells in vitro to aldehydes and non-aldehyde chemicals (nicotine, hydroquinone and 2,5-dimethylfuran) present in tobacco smoke and used microarrays to obtain a global view of the transcriptomic responses. We compared responses of the individual aldehydes with that of the non-aldehydes. We also studied the response of the aldehydes when present in a mixture at relative concentrations as present in cigarette smoke. Formaldehyde gave the strongest response; a total of 66 genes were more than 1.5-fold differentially expressed mostly involved in apoptosis and DNA damage related processes, followed by acetaldehyde (57 genes), hydroquinone (55 genes) and nicotine (8 genes). For acrolein and the mixture only one gene was upregulated involved in oxidative stress. No gene expression effect was found for exposure to 2,5-dimethylfuran. Overall, aldehyde responses are primarily indicative for genotoxicity and oxidative stress. These two toxicity mechanisms are linked to respiratory diseases such as cancer and COPD, respectively. The present findings could be important in providing further understanding of the role of aldehydes emitted from cigarette smoke in the onset of pulmonary diseases. Copyright © 2013 Elsevier Ltd. All rights reserved.

Acute cardiopulmonary toxicity of inhaled aldehydes: role of TRPA1

PubMed Central

Conklin, Daniel J.

2016-01-01

Inhalation of high-level volatile aldehydes, as present in smoke from wildfires and in tobacco smoke, is associated with both acute and chronic cardiopulmonary morbidity and mortality, but the underlying mechanisms are unclear. The transient receptor potential ankyrin 1 (TRPA1) protein forms a cation channel (irritant receptor) that mediates tobacco smoke–induced airway and lung injury, yet the role of TRPA1 in the cardiovascular toxicity of aldehyde exposure is unclear. Physiologically, airway-located TRPA1 activation triggers an irritant response (e.g., coughing and “respiratory braking”) that alters the rate and depth of breathing to reduce exposure. Acrolein (2-propenal), a volatile, unsaturated aldehyde, activates TRPA1. Acrolein was used as a chemical weapon in World War I and is present at high levels in wildfires and tobacco smoke. Acrolein is thought to contribute to pulmonary and cardiovascular injury caused by tobacco smoke exposure, although the role of TRPA1 in cardiovascular toxicity is unclear. This mini-review addresses this gap in our knowledge by exploring literature and recent data indicating a connection between TRPA1 and cardiovascular as well as pulmonary injury due to inhaled aldehydes. PMID:27152448

A Comparative Study of Basic, Amphoteric, and Acidic Catalysts in the Oxidative Coupling of Methanol and Ethanol for Acrolein Production.

PubMed

Lilić, Aleksandra; Wei, Tiantian; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

2017-09-11

The impact of acid/base properties (determined by adsorption microcalorimetry) of various catalysts on the cross-aldolization of acetaldehyde and formaldehyde leading to acrolein was methodically studied in oxidizing conditions starting from a mixture of methanol and ethanol. The aldol condensation and further dehydration to acrolein were carried out on catalysts presenting various acid/base properties (MgO, Mg-Al oxides, Mg/SiO 2 , NbP, and heteropolyanions on silica, HPA/SiO 2 ). Thermodynamic calculations revealed that cross-aldolization is always favored compared with self-aldolization of acetaldehyde, which leads to crotonaldehyde formation. The presence of strong basic sites is shown to be necessary, but a too high amount drastically increases CO x production. On strong acid sites, production of acrolein and carbon oxides (CO x ) does not increase with temperature. The optimal catalyst for this process should be amphoteric with a balanced acid/base cooperation of medium strength sites and a small amount (<100 μmol g -1 ) of very strong basic sites (Q diff >150 kJ mol -1 ). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidative damage in keratinocytes exposed to cigarette smoke and aldehydes.

PubMed

Avezov, Katia; Reznick, Abraham Z; Aizenbud, Dror

2014-06-01

Cigarette smoke (CS) is a significant environmental source of human exposure to chemically active saturated (acetaldehyde) and α,β-unsaturated aldehydes (acrolein) inducing protein carbonylation and dysfunction. The exposure of oral tissues to environmental hazards is immense, especially in smokers. The objectives of the current study were to examine the effect of aldehydes originating from CS on intracellular proteins of oral keratinocytes and to observe the antioxidant response in these cells. Intracellular protein carbonyl modification under CS, acrolein and acetaldehyde exposure in the HaCaT keratinocyte cell line, representing oral keratinocytes was examined by Western blot. Possible intracellular enzymatic dysfunction under the above conditions was examined by lactate dehydrogenase (LDH) activity assay. Oxidative stress response was investigated, by DCF (2,7-dichlorodihydrofluorescein) assay and GSH (glutathione) oxidation. Intracellular protein carbonyls increased 5.2 times after CS exposure and 2.7 times after exposure to 1 μmol of acrolein. DCF assay revealed an increase of fluorescence intensity 3.2 and 3.1 times after CS and acrolein exposure, respectively. CS caused a 72.5% decrease in intracellular GSH levels compared to controls. Activity of intracellular LDH was preserved. α,β-Unsaturated aldehydes from CS are capable of intracellular protein carbonylation and have a role in intracellular oxidative stress elevation in keratinocytes, probably due to the reduction in GSH levels. Copyright © 2014 Elsevier Ltd. All rights reserved.

Transient receptor potential ankyrin receptor 1 is a novel target for pro-tussive agents.

PubMed

Andrè, E; Gatti, R; Trevisani, M; Preti, D; Baraldi, P G; Patacchini, R; Geppetti, P

2009-11-01

The transient receptor potential ankyrin receptor 1 (TRPA1) is a cation channel, co-expressed with the pro-tussive transient receptor potential vanilloid type 1 (TRPV1) channel in primary sensory neurons. TRPA1 is activated by a series of irritant exogenous and endogenous alpha,beta-unsaturated aldehydes which seem to play a role in airway diseases. We investigated whether TRPA1 agonists provoke cough in guinea pigs and whether TRPA1 antagonists inhibit this response. Animals were placed in a Perspex box, and cough sounds were recorded and counted by observers unaware of the treatment used. Inhalation of two selective TRPA1 agonists, allyl isothiocyanate and cinnamaldehyde, dose-dependently caused cough in control guinea pigs, but not in those with airway sensory nerves desensitized by capsaicin. Coughs elicited by TRPA1 agonists were reduced by non-selective (camphor and gentamicin) and selective (HC-030031) TRPA1 antagonists, whereas they were unaffected by the TRPV1 antagonist, capsazepine. Acrolein and crotonaldehyde, two alpha,beta-unsaturated aldehydes recently identified as TRPA1 stimulants and contained in cigarette smoke, air pollution or produced endogenously by oxidative stress, caused a remarkable tussive effect, a response that was selectively inhibited by HC-030031. Part of the cough response induced by cigarette smoke inhalation was inhibited by HC-030031, suggesting the involvement of TRPA1. A novel pro-tussive pathway involves the TRPA1 channel, expressed by capsaicin-sensitive airway sensory nerves and is activated by a series of exogenous (cigarette smoke) and endogenous irritants. These results suggest TRPA1 may be a novel target for anti-tussive medicines.

Isotope-labeling studies on the formation pathway of acrolein during heat processing of oils.

PubMed

Ewert, Alice; Granvogl, Michael; Schieberle, Peter

2014-08-20

Acrolein (2-propenal) is classified as a foodborne toxicant and was shown to be present in significant amounts in heated edible oils. Up to now, its formation was mainly suggested to be from the glycerol part of triacylglycerides, although a clear influence of the unsaturation of the fatty acid moiety was also obvious in previous studies. To unequivocally clarify the role of the glycerol and the fatty acid parts in acrolein formation, two series of labeled triacylglycerides were synthesized: [(13)C(3)]-triacylglycerides of stearic, oleic, linoleic, and linolenic acid and [(13)C(54)]-triacylglycerides with labeled stearic, oleic, and linoleic acid, but with unlabeled glycerol. Heating of each of the seven intermediates singly in silicon oil and measurement of the formed amounts of labeled and unlabeled acrolein clearly proved the fatty acid backbone as the key precursor structure. Enzymatically synthesized pure linoleic acid and linolenic acid hydroperoxides were shown to be the key intermediates in acrolein formation, thus allowing the discussion of a radical-induced reaction pathway leading to the formation of the aldehyde. Surprisingly, although several oils contained high amounts of acrolein after heating, deep-fried foods themselves, such as donuts or French fries, were low in the aldehyde.

OPTIMIZING THE PAKS METHOD FOR MEASURING AIRBORNE ACROLEIN

EPA Science Inventory

Airborne acrolein is produced from the combustion of fuel and tobacco and is of concern due to its potential for respiratory tract irritation and other adverse health effects. DNPH active-sampling is a method widely used for sampling airborne aldehydes and ketones (carbonyls); ...

Deficiency of aldose reductase exacerbates early pressure overload-induced cardiac dysfunction and autophagy in mice.

PubMed

Baba, Shahid P; Zhang, Deqing; Singh, Mahavir; Dassanayaka, Sujith; Xie, Zhengzhi; Jagatheesan, Ganapathy; Zhao, Jingjing; Schmidtke, Virginia K; Brittian, Kenneth R; Merchant, Michael L; Conklin, Daniel J; Jones, Steven P; Bhatnagar, Aruni

2018-05-01

Pathological cardiac hypertrophy is associated with the accumulation of lipid peroxidation-derived aldehydes such as 4-hydroxy-trans-2-nonenal (HNE) and acrolein in the heart. These aldehydes are metabolized via several pathways, of which aldose reductase (AR) represents a broad-specificity route for their elimination. We tested the hypothesis that by preventing aldehyde removal, AR deficiency accentuates the pathological effects of transverse aortic constriction (TAC). We found that the levels of AR in the heart were increased in mice subjected to TAC for 2 weeks. In comparison with wild-type (WT), AR-null mice showed lower ejection fraction, which was exacerbated 2 weeks after TAC. Levels of atrial natriuretic peptide and myosin heavy chain were higher in AR-null than in WT TAC hearts. Deficiency of AR decreased urinary levels of the acrolein metabolite, 3-hydroxypropylmercapturic acid. Deletion of AR did not affect the levels of the other aldehyde-metabolizing enzyme - aldehyde dehydrogenase 2 in the heart, or its urinary product - (N-Acetyl-S-(2-carboxyethyl)-l-cystiene). AR-null hearts subjected to TAC showed increased accumulation of HNE- and acrolein-modified proteins, as well as increased AMPK phosphorylation and autophagy. Superfusion with HNE led to a greater increase in p62, LC3II formation, and GFP-LC3-II punctae formation in AR-null than WT cardiac myocytes. Pharmacological inactivation of JNK decreased HNE-induced autophagy in AR-null cardiac myocytes. Collectively, these results suggest that during hypertrophy the accumulation of lipid peroxidation derived aldehydes promotes pathological remodeling via excessive autophagy, and that metabolic detoxification of these aldehydes by AR may be essential for maintaining cardiac function during early stages of pressure overload. Published by Elsevier Ltd.

Inhalation toxicology. VII., Times to incapacitation and death for rats exposed continuously to atmospheric acrolein vapor.

DOT National Transportation Integrated Search

1986-05-01

Acrolein, an organic aldehyde (CH2=CH-CHO), is extremely irritating to the respiratory passages at very low concentrations. It is known to be present in the smoke from certain materials used in aircraft cabin interiors and could contribute, therefore...

Sustainable Production of o-Xylene from Biomass-Derived Pinacol and Acrolein.

PubMed

Hu, Yancheng; Li, Ning; Li, Guangyi; Wang, Aiqin; Cong, Yu; Wang, Xiaodong; Zhang, Tao

2017-07-21

o-Xylene (OX) is a large-volume commodity chemical that is conventionally produced from fossil fuels. In this study, an efficient and sustainable two-step route is used to produce OX from biomass-derived pinacol and acrolein. In the first step, the phosphotungstic acid (HPW)-catalyzed pinacol dehydration in 1-ethyl-3-methylimidazolium chloride ([emim]Cl) selectively affords 2,3-dimethylbutadiene. The high selectivity of this reaction can be ascribed to the H-bonding interaction between Cl - and the hydroxy group of pinacol. The stabilization of the carbocation intermediate by the surrounding anion Cl - may be another reason for the high selectivity. Notably, the good reusability of the HPW/[emim]Cl system can reduce the waste output and production cost. In the second step, OX is selectively produced by a Diels-Alder reaction of 2,3-dimethylbutadiene and acrolein, followed by a Pd/C-catalyzed decarbonylation/aromatization cascade in a one-pot fashion. The sustainable two-step process efficiently produces renewable OX in 79 % overall yield. Analogously, biomass-derived crotonaldehyde and pinacol can also serve as the feedstocks for the production of 1,2,4-trimethylbenzene. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cells deficient in the FANC/BRCA pathway are hypersensitive to plasma levels of formaldehyde.

PubMed

Ridpath, John R; Nakamura, Ayumi; Tano, Keizo; Luke, April M; Sonoda, Eiichiro; Arakawa, Hiroshi; Buerstedde, Jean-Marie; Gillespie, David A F; Sale, Julian E; Yamazoe, Mitsuyoshi; Bishop, Douglas K; Takata, Minoru; Takeda, Shunichi; Watanabe, Masami; Swenberg, James A; Nakamura, Jun

2007-12-01

Formaldehyde is an aliphatic monoaldehyde and is a highly reactive environmental human carcinogen. Whereas humans are continuously exposed to exogenous formaldehyde, this reactive aldehyde is a naturally occurring biological compound that is present in human plasma at concentrations ranging from 13 to 97 micromol/L. It has been well documented that DNA-protein crosslinks (DPC) likely play an important role with regard to the genotoxicity and carcinogenicity of formaldehyde. However, little is known about which DNA damage response pathways are essential for cells to counteract formaldehyde. In the present study, we first assessed the DNA damage response to plasma levels of formaldehyde using chicken DT40 cells with targeted mutations in various DNA repair genes. Here, we show that the hypersensitivity to formaldehyde is detected in DT40 mutants deficient in the BRCA/FANC pathway, homologous recombination, or translesion DNA synthesis. In addition, FANCD2-deficient DT40 cells are hypersensitive to acetaldehyde, but not to acrolein, crotonaldehyde, glyoxal, and methylglyoxal. Human cells deficient in FANCC and FANCG are also hypersensitive to plasma levels of formaldehyde. These results indicate that the BRCA/FANC pathway is essential to counteract DPCs caused by aliphatic monoaldehydes. Based on the results obtained in the present study, we are currently proposing that endogenous formaldehyde might have an effect on highly proliferating cells, such as bone marrow cells, as well as an etiology of cancer in Fanconi anemia patients.

Acrolein Microspheres Are Bonded To Large-Area Substrates

NASA Technical Reports Server (NTRS)

Rembaum, Alan; Yen, Richard C. K.

1988-01-01

Reactive cross-linked microspheres produced under influence of ionizing radiation in aqueous solutions of unsaturated aldehydes, such as acrolein, with sodium dodecyl sulfate. Diameters of spheres depend on concentrations of ingredients. If polystyrene, polymethylmethacrylate, or polypropylene object immersed in solution during irradiation, microspheres become attached to surface. Resulting modified surface has grainy coating with reactivity similar to free microspheres. Aldehyde-substituted-functional microspheres react under mild conditions with number of organic reagents and with most proteins. Microsphere-coated macrospheres or films used to immobilize high concentrations of proteins, enzymes, hormones, viruses, cells, and large number of organic compounds. Applications include separation techniques, clinical diagnostic tests, catalytic processes, and battery separators.

Acrolein with an alpha, beta-unsaturated Carbonyl Group Inhibits LPS-induced Homodimerization of Toll-like Receptor 4

USDA-ARS?s Scientific Manuscript database

Acrolein is a highly electrophilic a,ß-unsaturated aldehyde present in a number of environmental sources, especially cigarette smoke. It reacts strongly with the thiol groups of cysteine residues by Michael addition and has been reported to inhibit nuclear factor-kB (NF-kB) activation by lipopolysac...

Hybrid microspheres

NASA Technical Reports Server (NTRS)

Yen, Richard C. K. (Inventor); Rembaum, Alan (Inventor)

1985-01-01

Substrates, particularly inert synthetic organic resin beads (10) or sheet (12) such as polystyrene are coated with a covalently bound layer (24) of polyacrolein by irradiation a solution (14) of acrolein or other aldehyde with high intensity radiation. Individual microspheres (22) are formed which attach to the surface to form the aldehyde containing layer (24). The aldehyde groups can be converted to other functional groups by reaction with materials such as hydroxylamine. Adducts of proteins such as antibodies or enzymes can be formed by direct reaction with the surface aldehyde groups.

Acrolein Can Cause Cardiovascular Disease: A Review.

PubMed

Henning, Robert J; Johnson, Giffe T; Coyle, Jayme P; Harbison, Raymond D

2017-07-01

Acrolein is a highly reactive unsaturated aldehyde that is formed during the burning of gasoline and diesel fuels, cigarettes, woods and plastics. In addition, acrolein is generated during the cooking or frying of food with fats or oils. Acrolein is also used in the synthesis of many organic chemicals and as a biocide in agricultural and industrial water supply systems. The total emissions of acrolein in the United States from all sources are estimated to be 62,660 tons/year. Acrolein is classified by the Environmental Protection Agency as a high-priority air and water toxicant. Acrolein can exert toxic effects following inhalation, ingestion, and dermal exposures that are dose dependent. Cardiovascular tissues are particularly sensitive to the toxic effects of acrolein based primarily on in vitro and in vivo studies. Acrolein can generate free oxygen radical stress in the heart, decrease endothelial nitric oxide synthase phosphorylation and nitric oxide formation, form cytoplasmic and nuclear protein adducts with myocyte and vascular endothelial cell proteins and cause vasospasm. In this manner, chronic exposure to acrolein can cause myocyte dysfunction, myocyte necrosis and apoptosis and ultimately lead to cardiomyopathy and cardiac failure. Epidemiological studies of acrolein exposure and toxicity should be developed and treatment strategies devised that prevent or significantly limit acrolein cardiovascular toxicity.

Lithium prevents acrolein-induced neurotoxicity in HT22 mouse hippocampal cells.

PubMed

Huang, Yingjuan; Qin, Jian; Chen, Meihui; Chao, Xiaojuan; Chen, Ziwei; Ramassamy, Charles; Pi, Rongbiao; Jin, Minghua

2014-04-01

Acrolein is a highly electrophilic alpha, beta-unsaturated aldehyde to which humans are exposed in many situations and has been implicated in neurodegenerative diseases, such as Alzheimer's disease. Lithium is demonstrated to have neuroprotective and neurotrophic effects in brain ischemia, trauma, neurodegenerative disorders, and psychiatric disorders. Previously we have found that acrolein induced neuronal death in HT22 mouse hippocampal cells. In this study, the effects of lithium on the acrolein-induced neurotoxicity in HT22 cells as well as its mechanism(s) were investigated. We found that lithium protected HT22 cells against acrolein-induced damage by the attenuation of reactive oxygen species and the enhancement of the glutathione level. Lithium also attenuated the mitochondrial dysfunction caused by acrolein. Furthermore, lithium significantly increased the level of phospho-glycogen synthase kinase-3 beta (GSK-3β), the non-activated GSK-3β. Taken together, our findings suggest that lithium is a protective agent for acrolein-related neurotoxicity.

Quantification of aldehydes emissions from alternative and renewable aviation fuels using a gas turbine engine

NASA Astrophysics Data System (ADS)

Li, Hu; Altaher, Mohamed A.; Wilson, Chris W.; Blakey, Simon; Chung, Winson; Rye, Lucas

2014-02-01

In this research three renewable aviation fuel blends including two HEFA (Hydrotreated Ester and Fatty Acid) blends and one FAE (Fatty Acids Ethyl Ester) blend with conventional Jet A-1 along with a GTL (Gas To Liquid) fuel have been tested for their aldehydes emissions on a small gas turbine engine. Three strong ozone formation precursors: formaldehyde, acetaldehyde and acrolein were measured in the exhaust at different operational modes and compared to neat Jet A-1. The aim is to assess the impact of renewable and alternative aviation fuels on aldehydes emissions from aircraft gas turbine engines so as to provide informed knowledge for the future deployment of new fuels in aviation. The results show that formaldehyde was a major aldehyde species emitted with a fraction of around 60% of total measured aldehydes emissions for all fuels. Acrolein was the second major emitted aldehyde species with a fraction of ˜30%. Acetaldehyde emissions were very low for all the fuels and below the detention limit of the instrument. The formaldehyde emissions at cold idle were up to two to threefold higher than that at full power. The fractions of formaldehyde were 6-10% and 20% of total hydrocarbon emissions in ppm at idle and full power respectively and doubled on a g kg-1-fuel basis.

Characterization of an allylic/benzyl alcohol dehydrogenase from Yokenella sp. strain WZY002, an organism potentially useful for the synthesis of α,β-unsaturated alcohols from allylic aldehydes and ketones.

PubMed

Ying, Xiangxian; Wang, Yifang; Xiong, Bin; Wu, Tingting; Xie, Liping; Yu, Meilan; Wang, Zhao

2014-04-01

A novel whole-cell biocatalyst with high allylic alcohol-oxidizing activities was screened and identified as Yokenella sp. WZY002, which chemoselectively reduced the C=O bond of allylic aldehydes/ketones to the corresponding α,β-unsaturated alcohols at 30°C and pH 8.0. The strain also had the capacity of stereoselectively reducing aromatic ketones to (S)-enantioselective alcohols. The enzyme responsible for the predominant allylic/benzyl alcohol dehydrogenase activity was purified to homogeneity and designated YsADH (alcohol dehydrogenase from Yokenella sp.), which had a calculated subunit molecular mass of 36,411 Da. The gene encoding YsADH was subsequently expressed in Escherichia coli, and the purified recombinant YsADH protein was characterized. The enzyme strictly required NADP(H) as a coenzyme and was putatively zinc dependent. The optimal pH and temperature for crotonaldehyde reduction were pH 6.5 and 65°C, whereas those for crotyl alcohol oxidation were pH 8.0 and 55°C. The enzyme showed moderate thermostability, with a half-life of 6.2 h at 55°C. It was robust in the presence of organic solvents and retained 87.5% of the initial activity after 24 h of incubation with 20% (vol/vol) dimethyl sulfoxide. The enzyme preferentially catalyzed allylic/benzyl aldehydes as the substrate in the reduction of aldehydes/ketones and yielded the highest activity of 427 U mg(-1) for benzaldehyde reduction, while the alcohol oxidation reaction demonstrated the maximum activity of 79.9 U mg(-1) using crotyl alcohol as the substrate. Moreover, kinetic parameters of the enzyme showed lower Km values and higher catalytic efficiency for crotonaldehyde/benzaldehyde and NADPH than for crotyl alcohol/benzyl alcohol and NADP(+), suggesting the nature of being an aldehyde reductase.

Characterization of an Allylic/Benzyl Alcohol Dehydrogenase from Yokenella sp. Strain WZY002, an Organism Potentially Useful for the Synthesis of α,β-Unsaturated Alcohols from Allylic Aldehydes and Ketones

PubMed Central

Ying, Xiangxian; Wang, Yifang; Xiong, Bin; Wu, Tingting; Xie, Liping; Yu, Meilan

2014-01-01

A novel whole-cell biocatalyst with high allylic alcohol-oxidizing activities was screened and identified as Yokenella sp. WZY002, which chemoselectively reduced the C=O bond of allylic aldehydes/ketones to the corresponding α,β-unsaturated alcohols at 30°C and pH 8.0. The strain also had the capacity of stereoselectively reducing aromatic ketones to (S)-enantioselective alcohols. The enzyme responsible for the predominant allylic/benzyl alcohol dehydrogenase activity was purified to homogeneity and designated YsADH (alcohol dehydrogenase from Yokenella sp.), which had a calculated subunit molecular mass of 36,411 Da. The gene encoding YsADH was subsequently expressed in Escherichia coli, and the purified recombinant YsADH protein was characterized. The enzyme strictly required NADP(H) as a coenzyme and was putatively zinc dependent. The optimal pH and temperature for crotonaldehyde reduction were pH 6.5 and 65°C, whereas those for crotyl alcohol oxidation were pH 8.0 and 55°C. The enzyme showed moderate thermostability, with a half-life of 6.2 h at 55°C. It was robust in the presence of organic solvents and retained 87.5% of the initial activity after 24 h of incubation with 20% (vol/vol) dimethyl sulfoxide. The enzyme preferentially catalyzed allylic/benzyl aldehydes as the substrate in the reduction of aldehydes/ketones and yielded the highest activity of 427 U mg−1 for benzaldehyde reduction, while the alcohol oxidation reaction demonstrated the maximum activity of 79.9 U mg−1 using crotyl alcohol as the substrate. Moreover, kinetic parameters of the enzyme showed lower Km values and higher catalytic efficiency for crotonaldehyde/benzaldehyde and NADPH than for crotyl alcohol/benzyl alcohol and NADP+, suggesting the nature of being an aldehyde reductase. PMID:24509923

Lipidomic analysis for carbonyl species derived from fish oil using liquid chromatography-tandem mass spectrometry.

PubMed

Suh, Joon Hyuk; Niu, Yue S; Hung, Wei-Lun; Ho, Chi-Tang; Wang, Yu

2017-06-01

Lipid peroxidation gives rise to carbonyl species, some of which are reactive and play a role in the pathogenesis of numerous human diseases. Oils are ubiquitous sources that can be easily oxidized to generate these compounds under oxidative stress. In this present work, we developed a targeted lipidomic method for the simultaneous determination of thirty-five aldehydes and ketones derived from fish oil, the omega-3 fatty acid-rich source, by using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The analytes include highly toxic reactive carbonyl species (RCS) such as acrolein, crotonaldehyde, trans-4-hydroxy-2-hexenal (HHE), trans-4-hydroxy-2-nonenal (HNE), trans-4-oxo-2-nonenal (ONE), glyoxal and methylglyoxal, all of which are promising biomarkers of lipid peroxidation. They were formed using in vitro Fe(II)-mediated oxidation, and derivatized using 2,4-dinitrophenylhydrazine (DNPH) for the feasibility of quantitative assay. Before analysis, solid phase extraction (SPE) was used to clean samples further. Uniquely different patterns of carbonyl compound generation between omega-3 and 6 fatty acids were observed using this lipidomic approach. The method developed was both validated, and successfully applied to monitor formation of carbonyl species by lipid peroxidation using ten different fish oil products. Hypotheses of correlations between the monitored dataset of analytes and their parent fatty acids were also tested using the Pearson's correlation test. Results indicate our method is a useful analytical tool for lipid peroxidation studies. Copyright © 2017 Elsevier B.V. All rights reserved.

A Potential Role for Acrolein in Neutrophil-Mediated Chronic Inflammation.

PubMed

Noerager, Brett D; Xu, Xin; Davis, Virginia A; Jones, Caleb W; Okafor, Svetlana; Whitehead, Alicia; Blalock, J Edwin; Jackson, Patricia L

2015-12-01

Neutrophils (PMNs) are key mediators of inflammatory processes throughout the body. In this study, we investigated the role of acrolein, a highly reactive aldehyde that is ubiquitously present in the environment and produced endogenously at sites of inflammation, in mediating PMN-mediated degradation of collagen facilitating proline-glycine-proline (PGP) production. We treated peripheral blood neutrophils with acrolein and analyzed cell supernatants and lysates for matrix metalloproteinase-9 (MMP-9) and prolyl endopeptidase (PE), assessed their ability to break down collagen and release PGP, and assayed for the presence of leukotriene A4 hydrolase (LTA4H) and its ability to degrade PGP. Acrolein treatment induced elevated production and functionality of collagen-degrading enzymes and generation of PGP fragments. Meanwhile, LTA4H levels and triaminopeptidase activity declined with increasing concentrations of acrolein thereby sparing PGP from enzymatic destruction. These findings suggest that acrolein exacerbates the acute inflammatory response mediated by neutrophils and sets the stage for chronic pulmonary and systemic inflammation.

Acrolein acts as a neurotoxin in the nigrostriatal dopaminergic system of rat: involvement of α-synuclein aggregation and programmed cell death

PubMed Central

Wang, Yi-Ting; Lin, Hui-Ching; Zhao, Wei-Zhong; Huang, Hui-Ju; Lo, Yu-Li; Wang, Hsiang-Tsui; Maan-Yuh Lin, Anya

2017-01-01

Clinical studies report significant increases in acrolein (an α,β-unsaturated aldehyde) in the substantia nigra (SN) of patients with Parkinson’s disease (PD). In the present study, acrolein-induced neurotoxicity in the nigrostriatal dopaminergic system was investigated by local infusion of acrolein (15, 50, 150 nmoles/0.5 μl) in the SN of Sprague-Dawley rats. Acrolein-induced neurodegeneration of nigrostriatal dopaminergic system was delineated by reductions in tyrosine hydroxylase (TH) levels, dopamine transporter levels and TH-positive neurons in the infused SN as well as in striatal dopamine content. At the same time, apomorphine-induced turning behavior was evident in rats subjected to a unilateral infusion of acrolein in SN. Acrolein was pro-oxidative by increasing 4-hydroxy-2-nonenal and heme oxygenase-1 levels. Furthermore, acrolein conjugated with proteins at lysine residue and induced α-synuclein aggregation in the infused SN. Acrolein was pro-inflammatory by activating astrocytes and microglia. In addition, acrolein activated caspase 1 in the infused SN, suggesting acrolein-induced inflammasome formation. The neurotoxic mechanisms underlying acrolein-induced neurotoxicity involved programmed cell death, including apoptosis and necroptosis. Compared with well-known Parkinsonian neurotoxins, including 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine and rotenone which do not exist in the SN of PD patients, our in vivo study shows that acrolein acts as a Parkinsonian neurotoxin in the nigrostriatal dopaminergic system of rat brain. PMID:28401906

Uptake of aldehydes and ketones at typical indoor concentrations by houseplants.

PubMed

Tani, Akira; Hewitt, C Nicholas

2009-11-01

The uptake rates of low-molecular weight aldehydes and ketones by peace lily (Spathiphyllum clevelandii) and golden pothos (Epipremnum aureum) leaves at typical indoor ambient concentrations (10(1)-10(2) ppbv) were determined. The C3-C6 aldehydes and C4-C6 ketones were taken up by the plant leaves, but the C3 ketone acetone was not. The uptake rate normalized to the ambient concentration C(a) ranged from 7 to 19 mmol m(-2) s(-1) and from 2 to 7 mmol m(-2) s(-1) for the aldehydes and ketones, respectively. Longer-term fumigation results revealed that the total uptake amounts were 30-100 times as much as the amounts dissolved in the leaf, suggesting that volatile organic carbons are metabolized in the leaf and/or translocated through the petiole. The ratio of the intercellular concentration to the external (ambient) concentration (C(i)/C(a)) was significantly lower for most aldehydes than for most ketones. In particular, a linear unsaturated aldehyde, crotonaldehyde, had a C(i)/C(a) ratio of approximately 0, probably because of its highest solubility in water.

Silica nanoparticles as vehicles for therapy delivery in neurological injury

NASA Astrophysics Data System (ADS)

Schenk, Desiree

Acrolein, a very reactive aldehyde, is a culprit in the biochemical cascade after primary, mechanical spinal cord injury (SCI), which leads to the destruction of tissue initially unharmed, referred to as "secondary injury". Additionally, in models of multiple sclerosis (MS) and some clinical research, acrolein levels are significantly increased. This aldehyde overwhelms the natural anti-oxidant system, reacts freely with proteins, and releases during lipid peroxidation (LPO), effectively regenerating its self. Due to its ability to make more copies of itself in the presence of tissue via lipid peroxidation, researchers believe that acrolein plays a role in the increased destruction of the central nervous system in both SCI and MS. Hydralazine, an FDA-approved hypertension drug, has been shown to scavenge acrolein, but its side effects and short half life at the appropriate dose for acrolein scavenging must be improved for beneficial clinical translation. Due to the inefficient delivery of therapeutic drugs, nanoparticles have become a major field of exploration for medical applications. Based on their material properties, they can help treat disease by delivering drugs to specific tissues, enhancing detection methods, or a mixture of both. Nanoparticles made from silica provide distinct advantages. They form porous networks that can carry therapeutic molecules throughout the body. Therefore, a nanomedical approach has been designed using silica nanoparticles as a porous delivery vehicle hydralazine. The silica nanoparticles are formed in a one-step method that incorporates poly(ethylene) glycol (PEG), a stealth molecule, directly onto the nanoparticles. As an additional avenue for study, a natural product in green tea, epigallocatechin gallate (EGCG), has been explored for its ability to react with acrolein, disabling its reactive capabilities. Upon demonstration of attenuating acrolein, EGCG's delivery may also be improved using the nanomedical approach. The nanoparticles' physical characteristics were characterized and their interactions in vitro were studied for cytotoxicity and potential activity in attenuating neuronal damage.

Nonaggregating Microspheres Containing Aldehyde Groups

NASA Technical Reports Server (NTRS)

Rembaum, Alan

1989-01-01

Cobalt gamma irradiation of hydrophilic monomers in presence of acrolein yields exceptionally-stable, nonaggregating microspheres. Mixtures of 2-hydroxyethyl methacrylate (HEMA) and acrolein form homogeneous solutions in distilled water containing 0.4 percent polyethylene oxide (PEO). After deaeration with nitrogen, mixtures irradiated at room temperature with gamma rays from cobalt source; total exposure time 4 hours, at rate of 0.2 milliroentgen per hour. Reaction product centrifuged three times for purification and kept in distilled water.

Cigarette Filter Ventilation and Smoking Protocol Influence Aldehyde Smoke Yields

PubMed Central

2018-01-01

The WHO study group on tobacco product regulation (TobReg) advised regulating and lowering toxicant levels in cigarette smoke. Aldehydes are one of the chemical classes on the TobReg smoke toxicants priority list. To provide insight in factors determining aldehyde yields, the levels of 12 aldehydes in mainstream cigarette smoke of 11 Dutch brands were quantified. Variations in smoking behavior and cigarette design affecting human exposure to aldehydes were studied by using four different machine testing protocols. Machine smoking was based on the International Standardization Organization (ISO) and Health Canada Intense (HCI) regime, both with and without taping the filter vents. The 11 cigarette brands differed in (i) design and blend characteristics; (ii) tar, nicotine, and carbon monoxide (TNCO) levels; (iii) popularity; and (iv) manufacturer. Cigarette smoke was trapped on a Cambridge filter pad and carboxen cartridge. After being dissolved in methanol/CS2 and derivatization with DNPH, the aldehyde yields were determined using HPLC-DAD. Using an intense smoking regime (increased puff volume, shorter puff interval) significantly increased aldehyde yields, following the pattern: ISO < ISO-taped < HCI-untaped < HCI. For all of the regimes, acetaldehyde and acrolein yields were strongly correlated (r = 0.804). The difference in TNCO and aldehyde levels between regular and highly ventilated low-TNCO cigarettes (as measured using ISO) diminished when smoking intensely; this effect is stronger when combined with taping filter vents. The highly ventilated low-TNCO brands showed six times more aldehyde production per mg nicotine for the intense smoking regimes. In conclusion, acetaldehyde and acrolein can be used as representatives for the class of volatile aldehydes for the different brands and smoking regimes. The aldehyde-to-nicotine ratio increased when highly ventilated cigarettes were smoked intensely, similar to real smokers. Thus, a smoker of highly ventilated low-TNCO cigarettes has an increased potential for higher aldehyde exposures compared to a smoker of regular cigarettes. PMID:29727173

Development of an LC-MS/MS analytical method for the simultaneous measurement of aldehydes from polyunsaturated fatty acids degradation in animal feed.

PubMed

Douny, Caroline; Bayram, Pinar; Brose, François; Degand, Guy; Scippo, Marie-Louise

2016-05-01

Knowing that polyunsaturated fatty acids can lead to the formation of potentially toxic aldehydes as secondary oxidation products, an analytical method using liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) detection was developed to measure the concentration of eight aldehydes in animal feed: malondialdehyde (MDA), 4-hydroxy-2-nonenal (4-HNE), 4-hydroxy-2-hexenal (4-HHE), crotonaldehyde (CRT), benzaldehyde (BNZ), hexanal (HXL), 2,4-nonadienal, and 2,4-decadienal. The developed method was validated according to the criteria and procedure described in international standards. The evaluated parameters were specificity/selectivity, recovery, precision, accuracy, uncertainty, limits of detection and quantification, using the concept of accuracy profiles. These parameters were determined during experiments conducted over three different days with ground Kellogg's® Corn Flakes® cereals as model matrix for animal feed and spiked at different levels of concentration. Malondialdehyde, 4-HHE, 4-HNE, crotonaldehyde, benzaldehyde, and hexanal can be analyzed in the same run in animal feed with a very good accuracy, with recovery rates ranging from 86 to 109% for a working range going from 0.16 to 12.50 mg/kg. The analysis of 2,4-nonadienal and 2,4-decadienal can also be performed but in a limited range of concentration and with a limited degree of accuracy. Their recovery rates ranged between 54 and 114% and coefficient of variation for the intermediate precision between 11 and 25% for these two compounds. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Comparative Risks of Aldehyde Constituents in Cigarette Smoke Using Transient Computational Fluid Dynamics/Physiologically Based Pharmacokinetic Models of the Rat and Human Respiratory Tracts

PubMed Central

Corley, Richard A.; Kabilan, Senthil; Kuprat, Andrew P.; Carson, James P.; Jacob, Richard E.; Minard, Kevin R.; Teeguarden, Justin G.; Timchalk, Charles; Pipavath, Sudhakar; Glenny, Robb; Einstein, Daniel R.

2015-01-01

Computational fluid dynamics (CFD) modeling is well suited for addressing species-specific anatomy and physiology in calculating respiratory tissue exposures to inhaled materials. In this study, we overcame prior CFD model limitations to demonstrate the importance of realistic, transient breathing patterns for predicting site-specific tissue dose. Specifically, extended airway CFD models of the rat and human were coupled with airway region-specific physiologically based pharmacokinetic (PBPK) tissue models to describe the kinetics of 3 reactive constituents of cigarette smoke: acrolein, acetaldehyde and formaldehyde. Simulations of aldehyde no-observed-adverse-effect levels for nasal toxicity in the rat were conducted until breath-by-breath tissue concentration profiles reached steady state. Human oral breathing simulations were conducted using representative aldehyde yields from cigarette smoke, measured puff ventilation profiles and numbers of cigarettes smoked per day. As with prior steady-state CFD/PBPK simulations, the anterior respiratory nasal epithelial tissues received the greatest initial uptake rates for each aldehyde in the rat. However, integrated time- and tissue depth-dependent area under the curve (AUC) concentrations were typically greater in the anterior dorsal olfactory epithelium using the more realistic transient breathing profiles. For human simulations, oral and laryngeal tissues received the highest local tissue dose with greater penetration to pulmonary tissues than predicted in the rat. Based upon lifetime average daily dose comparisons of tissue hot-spot AUCs (top 2.5% of surface area-normalized AUCs in each region) and numbers of cigarettes smoked/day, the order of concern for human exposures was acrolein > formaldehyde > acetaldehyde even though acetaldehyde yields were 10-fold greater than formaldehyde and acrolein. PMID:25858911

Aldehydes in Relation to Air Pollution Sources: A Case Study around the Beijing Olympics

PubMed Central

Altemose, Brent; Gong, Jicheng; Zhu, Tong; Hu, Min; Zhang, Liwen; Cheng, Hong; Zhang, Lin; Tong, Jian; Kipen, Howard M.; Strickland, Pamela Ohman; Meng, Qingyu; Robson, Mark G.; Zhang, Junfeng

2015-01-01

This study was carried out to characterize three aldehydes of health concern (formaldehyde, acetaldehyde, and acrolein) at a central Beijing site in the summer and early fall of 2008 (from June to October). Aldehydes in polluted atmospheres come from both primary and secondary sources, which limits the control strategies for these reactive compounds. Measurements were made before, during, and after the Beijing Olympics to examine whether the dramatic air pollution control measures implemented during the Olympics had an impact on concentrations of the three aldehydes and their underlying primary and secondary sources. Average concentrations of formaldehyde, acetaldehyde and acrolein were 29.3±15.1 μg/m3, 27.1±15.7 μg/m3 and 2.3±1.0 μg/m3, respectively, for the entire period of measurements, all being at the high end of concentration ranges measured in cities around the world in photochemical smog seasons. Formaldehyde and acrolein increased during the pollution control period compared to the pre-Olympic Games, followed the changing pattern of temperature, and were significantly correlated with ozone and with a secondary formation factor identified by principal component analysis (PCA). In contrast, acetaldehyde had a reduction in mean concentration during the Olympic air pollution control period compared to the pre-Olympic period and was significantly correlated with several pollutants emitted from local emission sources (e.g., NO2, CO, and PM2.5). Acetaldehyde was also more strongly associated with primary emission sources including vegetative burning and oil combustion factors identified through the PCA. All three aldehydes were lower during the post-Olympic sampling period compared to the before and during Olympic periods, likely due to seasonal and regional effects. Our findings point to the complexity of source control strategies for secondary pollutants. PMID:25883528

Janus-faced Acrolein prevents allergy but accelerates tumor growth by promoting immunoregulatory Foxp3+ cells: Mouse model for passive respiratory exposure.

PubMed

Roth-Walter, Franziska; Bergmayr, Cornelia; Meitz, Sarah; Buchleitner, Stefan; Stremnitzer, Caroline; Fazekas, Judit; Moskovskich, Anna; Müller, Mario A; Roth, Georg A; Manzano-Szalai, Krisztina; Dvorak, Zdenek; Neunkirchner, Alina; Jensen-Jarolim, Erika

2017-03-23

Acrolein, a highly reactive unsaturated aldehyde, is generated in large amounts during smoking and is best known for its genotoxic capacity. Here, we aimed to assess whether acrolein at concentrations relevant for smokers may also exert immunomodulatory effects that could be relevant in allergy or cancer. In a BALB/c allergy model repeated nasal exposure to acrolein abrogated allergen-specific antibody and cytokine formation, and led to a relative accumulation of regulatory T cells in the lungs. Only the acrolein-treated mice were protected from bronchial hyperreactivity as well as from anaphylactic reactions upon challenge with the specific allergen. Moreover, grafted D2F2 tumor cells grew faster and intratumoral Foxp3+ cell accumulation was observed in these mice compared to sham-treated controls. Results from reporter cell lines suggested that acrolein acts via the aryl-hydrocarbon receptor which could be inhibited by resveratrol and 3'-methoxy-4'-nitroflavone Acrolein- stimulation of human PBMCs increased Foxp3+ expression by T cells which could be antagonized by resveratrol. Our mouse and human data thus revealed that acrolein exerts systemic immunosuppression by promoting Foxp3+ regulatory cells. This provides a novel explanation why smokers have a lower allergy, but higher cancer risk.

Acrolein cytotoxicity in hepatocytes involves endoplasmic reticulum stress, mitochondrial dysfunction and oxidative stress.

PubMed

Mohammad, Mohammad K; Avila, Diana; Zhang, Jingwen; Barve, Shirish; Arteel, Gavin; McClain, Craig; Joshi-Barve, Swati

2012-11-15

Acrolein is a common environmental, food and water pollutant and a major component of cigarette smoke. Also, it is produced endogenously via lipid peroxidation and cellular metabolism of certain amino acids and drugs. Acrolein is cytotoxic to many cell types including hepatocytes; however the mechanisms are not fully understood. We examined the molecular mechanisms underlying acrolein hepatotoxicity in primary human hepatocytes and hepatoma cells. Acrolein, at pathophysiological concentrations, caused a dose-dependent loss of viability of hepatocytes. The death was apoptotic at moderate and necrotic at high concentrations of acrolein. Acrolein exposure rapidly and dramatically decreased intracellular glutathione and overall antioxidant capacity, and activated the stress-signaling MAP-kinases JNK, p42/44 and p38. Our data demonstrate for the first time in human hepatocytes, that acrolein triggered endoplasmic reticulum (ER) stress and activated eIF2α, ATF-3 and -4, and Gadd153/CHOP, resulting in cell death. Notably, the protective/adaptive component of ER stress was not activated, and acrolein failed to up-regulate the protective ER-chaperones, GRP78 and GRP94. Additionally, exposure to acrolein disrupted mitochondrial integrity/function, and led to the release of pro-apoptotic proteins and ATP depletion. Acrolein-induced cell death was attenuated by N-acetyl cysteine, phenyl-butyric acid, and caspase and JNK inhibitors. Our data demonstrate that exposure to acrolein induces a variety of stress responses in hepatocytes, including GSH depletion, oxidative stress, mitochondrial dysfunction and ER stress (without ER-protective responses) which together contribute to acrolein toxicity. Our study defines basic mechanisms underlying liver injury caused by reactive aldehyde pollutants such as acrolein. Copyright © 2012 Elsevier Inc. All rights reserved.

Proteomic analysis of rat cerebral cortex following subchronic acrolein toxicity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rashedinia, Marzieh; Lari, Parisa; Abnous, Khalil, E-mail: Abnouskh@mums.ac.r

2013-10-01

Acrolein, a member of reactive α,β-unsaturated aldehydes, is a major environmental pollutant. Acrolein is also produced endogenously as a toxic by-product of lipid peroxidation. Because of high reactivity, acrolein may mediate oxidative damages to cells and tissues. It has been shown to be involved in a wide variety of pathological states including pulmonary, atherosclerosis and neurodegenerative diseases. In this study we employed proteomics approach to investigate the effects of subchronic oral exposures to 3 mg/kg of acrolein on protein expression profile in the brain of rats. Moreover effects of acrolein on malondialdehyde (MDA) levels and reduced glutathione (GSH) content weremore » investigated. Our results revealed that treatment with acrolein changed levels of several proteins in diverse physiological process including energy metabolism, cell communication and transport, response to stimulus and metabolic process. Interestingly, several differentially over-expressed proteins, including β-synuclein, enolase and calcineurin, are known to be associated with human neurodegenerative diseases. Changes in the levels of some proteins were confirmed by Western blot. Moreover, acrolein increases the level of MDA, as a lipid peroxidation biomarker and decreased GSH concentrations, as a non-enzyme antioxidant in the brain of acrolein treated rats. These findings suggested that acrolein induces the oxidative stress and lipid peroxidation in the brain, and so that may contribute to the pathophysiology of neurological disorders. - Highlights: • Acrolein intoxication increased lipid peroxidation and deplete GSH in rat brain. • Effect of acrolein on protein levels of cerebral cortex was analyzed by 2DE-PAGE. • Levels of a number of proteins with different biological functions were increased.« less

Acrolein cytotoxicity in hepatocytes involves endoplasmic reticulum stress, mitochondrial dysfunction and oxidative stress

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mohammad, Mohammad K.; Alcohol Research Center, University of Louisville; Avila, Diana

2012-11-15

Acrolein is a common environmental, food and water pollutant and a major component of cigarette smoke. Also, it is produced endogenously via lipid peroxidation and cellular metabolism of certain amino acids and drugs. Acrolein is cytotoxic to many cell types including hepatocytes; however the mechanisms are not fully understood. We examined the molecular mechanisms underlying acrolein hepatotoxicity in primary human hepatocytes and hepatoma cells. Acrolein, at pathophysiological concentrations, caused a dose-dependent loss of viability of hepatocytes. The death was apoptotic at moderate and necrotic at high concentrations of acrolein. Acrolein exposure rapidly and dramatically decreased intracellular glutathione and overall antioxidantmore » capacity, and activated the stress-signaling MAP-kinases JNK, p42/44 and p38. Our data demonstrate for the first time in human hepatocytes, that acrolein triggered endoplasmic reticulum (ER) stress and activated eIF2α, ATF-3 and -4, and Gadd153/CHOP, resulting in cell death. Notably, the protective/adaptive component of ER stress was not activated, and acrolein failed to up-regulate the protective ER-chaperones, GRP78 and GRP94. Additionally, exposure to acrolein disrupted mitochondrial integrity/function, and led to the release of pro-apoptotic proteins and ATP depletion. Acrolein-induced cell death was attenuated by N-acetyl cysteine, phenyl-butyric acid, and caspase and JNK inhibitors. Our data demonstrate that exposure to acrolein induces a variety of stress responses in hepatocytes, including GSH depletion, oxidative stress, mitochondrial dysfunction and ER stress (without ER-protective responses) which together contribute to acrolein toxicity. Our study defines basic mechanisms underlying liver injury caused by reactive aldehyde pollutants such as acrolein. -- Highlights: ► Human primary hepatocytes and cultured cell lines are used. ► Multiple cell death signaling pathways are activated by acrolein. ► Novel finding of acrolein-induced ER stress ► Acrolein fails to activate ER stress-induced protective responses. ► Combinatorial therapies may be needed for preventing acrolein hepatotoxicity.« less

Role of TRPA1 in acute cardiopulmonary toxicity of inhaled acrolein.

PubMed

Conklin, Daniel J; Haberzettl, Petra; Jagatheesan, Ganapathy; Kong, Maiying; Hoyle, Gary W

2017-06-01

Acrolein is a highly toxic, volatile, unsaturated aldehyde generated during incomplete combustion as in tobacco smoke and indoor fires. Because the transient receptor potential ankyrin 1 (TRPA1) channel mediates tobacco smoke-induced lung injury, we assessed its role in high-level acrolein-induced toxicity in mice. Acrolein (100-275ppm, 10-30min) caused upper airway epithelial sloughing, bradypnea and oral gasping, hypothermia, cardiac depression and mortality. Male wild-type mice (WT, C57BL/6; 5-52weeks) were significantly more sensitive to high-level acrolein than age-matched, female WT mice. Both male and female TRPA1-null mice were more sensitive to acrolein-induced mortality than age- and sex-matched WT mice. Acrolein exposure increased lung weight:body weight ratios and lung albumin and decreased plasma albumin to a greater extent in TRPA1-null than in WT mice. Lung and plasma protein-acrolein adducts were not increased in acrolein-exposed TRPA1-null mice compared with WT mice. To assess TRPA1-dependent protective mechanisms, respiratory parameters were monitored by telemetry. TRPA1-null mice had a slower onset of breathing rate suppression ('respiratory braking') than WT mice suggesting TRPA1 mediates this protective response. Surprisingly, WT male mice treated either with a TRPA1 antagonist (HC030031; 200mg/kg) alone or with combined TRPA1 (100mg/kg) and TRPV1 (capsazepine, 10mg/kg) antagonists at 30min post-acrolein exposure (i.e., "real world" delay in treatment) were significantly protected from acrolein-induced mortality. These data show TRPA1 protects against high-level acrolein-induced toxicity in a sex-dependent manner. Post-exposure TRPA1 antagonism also protected against acrolein-induced mortality attesting to a complex role of TRPA1 in cardiopulmonary injury. Copyright © 2016 Elsevier Inc. All rights reserved.

E-cigarettes generate high levels of aldehydes only in 'dry puff' conditions.

PubMed

Farsalinos, Konstantinos E; Voudris, Vassilis; Poulas, Konstantinos

2015-08-01

Aldehydes are emitted by electronic cigarettes due to thermal decomposition of liquid components. Although elevated levels have been reported with new-generation high-power devices, it is unclear whether they are relevant to true exposure of users (vapers) because overheating produces an unpleasant taste, called a dry puff, which vapers learn to avoid. The aim was to evaluate aldehyde emissions at different power levels associated with normal and dry puff conditions. Two customizable atomizers were prepared so that one (A1) had a double wick, resulting in high liquid supply and lower chance of overheating at high power levels, while the other (A2) was a conventional setup (single wick). Experienced vapers took 4-s puffs at 6.5 watts (W), 7.5 W, 9 W and 10 W power levels with both atomizers and were asked to report whether dry puffs were generated. The atomizers were then attached to a smoking machine and aerosol was trapped. Clinic office and analytical chemistry laboratory in Greece. Seven experienced vapers. Aldehyde levels were measured in the aerosol. All vapers identified dry puff conditions at 9 W and 10 W with A2. A1 did not lead to dry puffs at any power level. Minimal amounts of aldehydes per 10 puffs were found at all power levels with A1 (up to 11.3 µg for formaldehyde, 4.5 µg for acetaldehyde and 1.0 µg for acrolein) and at 6.5 W and 7.5 W with A2 (up to 3.7 µg for formaldehyde, 0.8 µg for acetaldehyde and 1.3 µg for acrolein). The levels were increased by 30 to 250 times in dry puff conditions (up to 344.6 µg for formaldehyde, 206.3 µg for acetaldehyde and 210.4 µg for acrolein, P < 0.001), while acetone was detected only in dry puff conditions (up to 22.5 µg). Electronic cigarettes produce high levels of aldehyde only in dry puff conditions, in which the liquid overheats, causing a strong unpleasant taste that e-cigarette users detect and avoid. Under normal vaping conditions aldehyde emissions are minimal, even in new-generation high-power e-cigarettes. © 2015 Society for the Study of Addiction.

Selected carbonyl compounds in the air of Silesia region

NASA Astrophysics Data System (ADS)

Czaplicka, Marianna; Chrobok, Michał

2018-01-01

This study was carried out to characterize three aldehydes of health concern (formaldehyde, acetaldehyde, and acrolein) at a three sites in Silesian region (Poland) in January and June 2015. Aldehydes in polluted atmospheres comes from both primary and secondary sources, which limits the control strategies for these reactive compounds. Average aldehyde concentration in summer period lies in range from 3.13 μg/m3 to 10.43 μg/m3, in winter period in range from 29.0 μg/m3 to 32.2 μg/m3. Acetaldehyde was dominant compound in winter period, in summer formaldehyde concentration was highest of all determined aldehydes.

Sulforaphane protects against acrolein-induced oxidative stress and inflammatory responses: modulation of Nrf-2 and COX-2 expression.

PubMed

Qin, Wang-Sen; Deng, Yu-Hui; Cui, Fa-Cai

2016-08-01

Acrolein (2-propenal) is a reactive α, β-unsaturated aldehyde which causes a health hazard to humans. The present study focused on determining the protection offered by sulforaphane against acrolein-induced damage in peripheral blood mononuclear cells (PBMC). Acrolein-induced oxidative stress was determined through evaluating the levels of reactive oxygen species, protein carbonyl and sulfhydryl content, thiobarbituric acid reactive species, total oxidant status and antioxidant status (total antioxidant capacity, glutathione, superoxide dismutase, catalase, glutathione peroxidase, glutathione-S-transferase activity). Also, Nrf-2 expression levels were determined using western blot analysis. Acrolein-induced inflammation was determined through analyzing expression of cyclooxygenase-2 by western blot and PGE2 levels by ELISA. The protection offered by sulforaphane against acrolein-induced oxidative stress and inflammation was studied. Acrolein showed a significant (p < 0.001) increase in the levels of oxidative stress parameters and down-regulated Nrf-2 expression. Acrolein-induced inflammation was observed through upregulation (p < 0.001) of COX-2 and PGE2 levels. Pretreatment with sulforaphane enhanced the antioxidant status through upregulating Nrf-2 expression (p < 0.001) in PBMC. Acrolein-induced inflammation was significantly inhibited through suppression of COX-2 (p < 0.001) and PGE2 levels (p < 0.001). The present study provides clear evidence that pre-treatment with sulforaphane completely restored the antioxidant status and prevented inflammatory responses mediated by acrolein. Thus the protection offered by sulforaphane against acrolein-induced damage in PBMC is attributed to its anti-oxidant and anti-inflammatory potential.

Mediating the potent ROS toxicity of acrolein in neurons with silica nanoparticles and a natural product approach

NASA Astrophysics Data System (ADS)

White-Schenk, Désirée.; Shi, Riyi; Leary, James F.

2014-03-01

Acrolein, a very reactive aldehyde, is a culprit in the biochemical cascade after primary, mechanical spinal cord injury (SCI), which leads to the destruction of tissue initially unharmed, referred to as "secondary injury". Additionally, in models of multiple sclerosis (MS) and some clinical research, acrolein levels are significantly increased. Due to its ability to make more copies of itself in the presence of tissue via lipid peroxidation, researchers believe that acrolein plays a role in the increased destruction of the central nervous system in both SCI and MS. Hydralazine, an FDAapproved hypotensive drug, has been shown to scavenge acrolein, but its side effects and short half life at the appropriate dose for acrolein scavenging must be improved for beneficial clinical translation. Therefore, a nanomedical approach has been designed using silica nanoparticles as a porous delivery vehicle hydralazine. The silica particles are formed in a one-step method that incorporates poly(ethylene) glycol (PEG), a stealth molecule, directly onto the nanoparticles. As an additional avenue for study, a natural product in green tea, epigallocatechin gallate (EGCG), has been explored for its ability to react with acrolein, disabling its reactive capabilities. Upon demonstration of attenuating acrolein, EGCG's delivery may also be improved using the nanomedical approach. The current work exposes the potential of using silica nanoparticles as a delivery vehicle and EGCG's antioxidant capabilities in B35 neuroblastoma cells exposed to acrolein. We also measure nanotoxicity to individual rat neurons using high-throughput image scanning cytometry.

Acrolein oxidizes the cytosolic and mitochondrial thioredoxins in human endothelial cells.

PubMed

Szadkowski, Adam; Myers, Charles R

2008-01-14

Acrolein is a reactive aldehyde that is a widespread environmental pollutant and can be generated endogenously from lipid peroxidation. The thioredoxin (Trx) system in endothelial cells plays a major role in the maintenance of cellular thiol redox balance, and is critical for cell survival. Normally, cells maintain the cytosolic (Trx1) and mitochondrial (Trx2) thioredoxins largely in the reduced state. In human microvascular endothelial cells, Trx1 was more sensitive than Trx2 to oxidation by acrolein. A 30-min exposure to 2.5 microM acrolein caused partial oxidation of Trx1 but not Trx2. The active site dithiol of Trx1 was essentially completely oxidized by 5 microM acrolein whereas 12.5 microM was required for complete oxidation of Trx2. Partial recovery of the Trx1 redox status was observed over a 4h acrolein-free recovery period, with increases in the reduced form and decreases in the fully oxidized form. For cells treated with 2.5 or 5 microM acrolein the recovery did not require protein synthesis, whereas protein synthesis was required for the return of reduced Trx1 in cells treated with 12.5 microM acrolein. Pretreatment of cells with N-acetylcysteine (NAC) resulted in partial protection of Trx1 from oxidation by acrolein. In cells treated with acrolein for 30 min, followed by a 14- to 16-h acrolein-free period, small but significant cytotoxic effects were observed with 2.5 microM acrolein whereas all cells were adversely affected by >or= 12.5 microM. NAC pretreatment significantly decreased the percentage of stressed cells subsequently exposed to 5 or 12.5 microM acrolein. Given the critical role of the thioredoxins in cell survival, the ability of acrolein to oxidize both thioredoxins should be taken into account for a thorough understanding of its cytotoxic effects.

Acrolein increases macrophage atherogenicity in association with gut microbiota remodeling in atherosclerotic mice: protective role for the polyphenol-rich pomegranate juice.

PubMed

Rom, Oren; Korach-Rechtman, Hila; Hayek, Tony; Danin-Poleg, Yael; Bar, Haim; Kashi, Yechezkel; Aviram, Michael

2017-04-01

The unsaturated aldehyde acrolein is pro-atherogenic, and the polyphenol-rich pomegranate juice (PJ), known for its anti-oxidative/anti-atherogenic properties, inhibits macrophage foam cell formation, the hallmark feature of early atherosclerosis. This study aimed to investigate two unexplored areas of acrolein atherogenicity: macrophage lipid metabolism and the gut microbiota composition. The protective effects of PJ against acrolein atherogenicity were also evaluated. Atherosclerotic apolipoprotein E-deficient (apoE -/- ) mice that were fed acrolein (3 mg/kg/day) for 1 month showed significant increases in serum and aortic cholesterol, triglycerides, and lipid peroxides. In peritoneal macrophages isolated from the mice and in J774A.1 cultured macrophages, acrolein exposure increased intracellular oxidative stress and stimulated cholesterol and triglyceride accumulation via enhanced rates of their biosynthesis and over-expression of key regulators of cellular lipid biosynthesis: sterol regulatory element-binding proteins (SREBPs), 3-hydroxy-3-methyl-glutaryl-CoA reductase (HMGCR), and diacylglycerol acyltransferase1 (DGAT1). Acrolein-fed mice demonstrated a major shift in the gut microbiota composition, including a significant phylum-level change in increased Firmicutes and decreased Bacteroidetes. At the family level, acrolein significantly increased the prevalence of Ruminococcaceae and Lachnospiraceae of which the Coprococcus genus was significantly and positively correlated with serum, aortic and macrophage lipid levels and peroxidation. The pro-atherogenic effects of acrolein on serum, aortas, macrophages, and the gut microbiota were substantially abolished by PJ. In conclusion, these findings provide novel mechanisms by which acrolein increases macrophage lipid accumulation and alters the gut microbiota composition in association with enhanced atherogenesis. Moreover, PJ was found as an effective strategy against acrolein atherogenicity.

Role of TRPA1 in acute cardiopulmonary toxicity of inhaled acrolein

DOE Office of Scientific and Technical Information (OSTI.GOV)

Conklin, Daniel J., E-mail: dj.conklin@louisville.

Acrolein is a highly toxic, volatile, unsaturated aldehyde generated during incomplete combustion as in tobacco smoke and indoor fires. Because the transient receptor potential ankyrin 1 (TRPA1) channel mediates tobacco smoke-induced lung injury, we assessed its role in high-level acrolein-induced toxicity in mice. Acrolein (100–275 ppm, 10–30 min) caused upper airway epithelial sloughing, bradypnea and oral gasping, hypothermia, cardiac depression and mortality. Male wild-type mice (WT, C57BL/6; 5–52 weeks) were significantly more sensitive to high-level acrolein than age-matched, female WT mice. Both male and female TRPA1-null mice were more sensitive to acrolein-induced mortality than age- and sex-matched WT mice. Acroleinmore » exposure increased lung weight:body weight ratios and lung albumin and decreased plasma albumin to a greater extent in TRPA1-null than in WT mice. Lung and plasma protein-acrolein adducts were not increased in acrolein-exposed TRPA1-null mice compared with WT mice. To assess TRPA1-dependent protective mechanisms, respiratory parameters were monitored by telemetry. TRPA1-null mice had a slower onset of breathing rate suppression (‘respiratory braking’) than WT mice suggesting TRPA1 mediates this protective response. Surprisingly, WT male mice treated either with a TRPA1 antagonist (HC030031; 200 mg/kg) alone or with combined TRPA1 (100 mg/kg) and TRPV1 (capsazepine, 10 mg/kg) antagonists at 30 min post-acrolein exposure (i.e., “real world” delay in treatment) were significantly protected from acrolein-induced mortality. These data show TRPA1 protects against high-level acrolein-induced toxicity in a sex-dependent manner. Post-exposure TRPA1 antagonism also protected against acrolein-induced mortality attesting to a complex role of TRPA1 in cardiopulmonary injury. - Highlights: • TRPA1 protects mice against toxicity and mortality of inhaled high-level acrolein. • TRPA1 protection against inhaled high-level acrolein is sex-dependent in mice. • Age (5–52 weeks old) was not a determinant of acrolein-induced mortality in mice. • TRPA1 antagonist is protective after inhaled high-level acrolein in male mice.« less

Aldehyde levels in e-cigarette aerosol: Findings from a replication study and from use of a new-generation device.

PubMed

Farsalinos, Konstantinos E; Kistler, Kurt A; Pennington, Alexander; Spyrou, Alketa; Kouretas, Dimitris; Gillman, Gene

2018-01-01

A recent study identified high aldehyde emissions from e-cigarettes (ECs), that when converted to reasonable daily human EC liquid consumption, 5 g/day, gave formaldehyde exposure equivalent to 604-3257 tobacco cigarettes. We replicated this study and also tested a new-generation atomizer under verified realistic (no dry puff) conditions. CE4v2 atomizers were tested at 3.8 V and 4.8 V, and a Nautilus Mini atomizer was tested at 9.0 W and 13.5 W. All measurements were performed in a laboratory ISO-accredited for EC aerosol collection and aldehyde measurements. CE4v2 generated dry puffs at both voltage settings. Formaldehyde levels were >10-fold lower, acetaldehyde 6-9-fold lower and acrolein 16-26-fold lower than reported in the previous study. Nautilus Mini did not generate dry puffs, and minimal aldehydes were emitted despite >100% higher aerosol production per puff compared to CE4v2 (formaldehyde: 16.7 and 16.5 μg/g; acetaldehyde: 9.6 and 10.3 μg/g; acrolein: 8.6 and 11.7 μg/g at 9.0 W and 13.5 W, respectively). EC liquid consumption of 5 g/day reduces aldehyde exposure by 94.4-99.8% compared to smoking 20 tobacco cigarettes. Checking for dry puffs is essential for EC emission testing. Under realistic conditions, new-generation ECs emit minimal aldehydes/g liquid at both low and high power. Validated methods should be used when analyzing EC aerosol. Copyright © 2017 Elsevier Ltd. All rights reserved.

Role of Lipid Peroxidation-Derived α, β-Unsaturated Aldehydes in Vascular Dysfunction

PubMed Central

Lee, Seung Eun; Park, Yong Seek

2013-01-01

Vascular diseases are the most prominent cause of death, and inflammation and vascular dysfunction are key initiators of the pathophysiology of vascular disease. Lipid peroxidation products, such as acrolein and other α, β-unsaturated aldehydes, have been implicated as mediators of inflammation and vascular dysfunction. α, β-Unsaturated aldehydes are toxic because of their high reactivity with nucleophiles and their ability to form protein and DNA adducts without prior metabolic activation. This strong reactivity leads to electrophilic stress that disrupts normal cellular function. Furthermore, α, β-unsaturated aldehydes are reported to cause endothelial dysfunction by induction of oxidative stress, redox-sensitive mechanisms, and inflammatory changes such as induction of cyclooxygenase-2 and cytokines. This review provides an overview of the effects of lipid peroxidation products, α, β-unsaturated aldehydes, on inflammation and vascular dysfunction. PMID:23819013

Acrolein-induced activation of mitogen-activated protein kinase signaling is mediated by alkylation of thioredoxin reductase and thioredoxin 1.

PubMed

Randall, Matthew J; Spiess, Page C; Hristova, Milena; Hondal, Robert J; van der Vliet, Albert

2013-01-01

Cigarette smoking remains a major health concern worldwide, and many of the adverse effects of cigarette smoke (CS) can be attributed to its abundant electrophilic aldehydes, such as acrolein (2-propenal). Previous studies indicate that acrolein readily reacts with thioredoxin reductase 1 (TrxR1), a critical enzyme involved in regulation of thioredoxin (Trx)-mediated redox signaling, by alkylation at its selenocysteine (Sec) residue. Because alkylation of Sec within TrxR1 has significant implications for its enzymatic function, we explored the potential importance of TrxR1 alkylation in acrolein-induced activation or injury of bronchial epithelial cells. Exposure of human bronchial epithelial HBE1 cells to acrolein (1-30 μM) resulted in dose-dependent loss of TrxR thioredoxin reductase activity, which coincided with its alkylation, as determined by biotin hydrazide labeling, and was independent of initial GSH status. To test the involvement of TrxR1 in acrolein responses in HBE1 cells, we suppressed TrxR1 using siRNA silencing or augmented TrxR1 by cell supplementation with sodium selenite. Acrolein exposure of HBE1 cells induced dose-dependent activation of the MAP kinases, extracellular regulated kinase (ERK), c-Jun N-terminal kinase (JNK), and p38, and activation of JNK was markedly enhanced after selenite-mediated induction of TrxR1, and was associated with increased alkylation of TrxR1. Conversely, siRNA silencing of TrxR1 significantly suppressed the ability of acrolein to activate JNK, and also appeared to attenuate acrolein-dependent activation of ERK and p38. Alteration of initial TrxR1 levels by siRNA or selenite supplementation also affected initial Trx1 redox status and acrolein-mediated alkylation of Trx1, but did not significantly affect acrolein-mediated activation of HO-1 or cytotoxicity. Collectively, our findings indicate that alkylation of TrxR1 and/or Trx1 may contribute directly to acrolein-mediated activation of MAP kinases such as JNK, and may therefore be important in acrolein-induced alterations in airway epithelial function, as a contributing mechanism in tobacco-related respiratory disease.

Critical role of aldehydes in cigarette smoke-induced acute airway inflammation

PubMed Central

2013-01-01

Background Cigarette smoking (CS) is the most important risk factor for COPD, which is associated with neutrophilic airway inflammation. We hypothesize, that highly reactive aldehydes are critical for CS-induced neutrophilic airway inflammation. Methods BALB/c mice were exposed to CS, water filtered CS (WF-CS) or air for 5 days. Levels of total particulate matter (TPM) and aldehydes in CS and WF-CS were measured. Six hours after the last exposure, inflammatory cells and cytokine levels were measured in lung tissue and bronchoalveolar lavage fluid (BALF). Furthermore, Beas-2b bronchial epithelial cells were exposed to CS extract (CSE) or WF-CS extract (WF-CSE) in the absence or presence of the aldehyde acrolein and IL-8 production was measured after 24 hrs. Results Compared to CS, in WF-CS strongly decreased (CS; 271.1 ± 41.5 μM, WF-CS; 58.5 ± 8.2 μM) levels of aldehydes were present whereas levels of TPM were only slightly reduced (CS; 20.78 ± 0.59 mg, WF-CS; 16.38 ± 0.36 mg). The numbers of mononuclear cells in BALF (p<0.01) and lung tissue (p<0.01) were significantly increased in the CS- and WF-CS-exposed mice compared to air control mice. Interestingly, the numbers of neutrophils (p<0.001) in BALF and neutrophils and eosinophils (p<0.05) in lung tissue were significantly increased in the CS-exposed but not in WF-CS-exposed mice as compared to air control mice. Levels of the neutrophil and eosinophil chemoattractants KC, MCP-1, MIP-1α and IL-5 were all significantly increased in lung tissue from CS-exposed mice compared to both WF-CS-exposed and air control mice. Interestingly, depletion of aldehydes in WF-CS extract significantly reduced IL-8 production in Beas-2b as compared to CSE, which could be restored by the aldehyde acrolein. Conclusion Aldehydes present in CS play a critical role in inflammatory cytokine production and neutrophilic- but not mononuclear airway inflammation. PMID:23594194

Technical note: Concerns regarding 24-h sampling for formaldehyde, acetaldehyde, and acrolein using 2,4-dintrophenylhydrazine (DNPH)-coated solid sorbents

EPA Science Inventory

A wide variety of natural and anthropogenic sources emit airborne carbonyls such as aldehydes (RCHO) and ketones (R1COR2). Vegetation, food, forest fires, fossil fuel combustion, disinfectants, fumigants, preservatives, and resins are a few examples of primary carbonyl sources. T...

Technical Note: Concerns regarding 24-h sampling for formaldehyde, acetaldehyde, and acrolein using 2,4-dinitrophenylhydrazine (DNPH)-coated solid sorbents

EPA Science Inventory

A wide variety of natural and anthropogenic sources emit airborne carbonyls such as aldehydes (RCHO) and ketones (R1COR2). Vegetation, food, forest fires, fossil fuel combustion, disinfectants, fumigants, preservatives, and resins are a few examples of primary carbonyl sources. T...

Co-exposure to inhaled ambient particulate matter and acrolein alters myocardial synchrony in mice: evidence for TRPA1 involvement

EPA Science Inventory

Because air pollution is a complex mixture of constituents, often including particulates and aldehydes, attributing health effects to air pollutants in a given ambient air shed can be difficult when pollutants are studied in isolation. The purpose of this study was to examine the...

How irritating: the role of TRPA1 in sensing cigarette smoke and aerogenic oxidants in the airways

PubMed Central

Simon, Sidney A.; Liedtke, Wolfgang

2008-01-01

Airway irritants cause a variety of lung pathologies. Two separate studies, the first recently reported in the JCI by Bessac et al. and the second reported by Andrè et al. in the current issue of the JCI (see the related article beginning on page 2574), have identified irritants that activate transient receptor potential cation channel, subfamily A, member 1 (TRPA1) receptors in airway sensory neurons, resulting in neurogenic inflammation and respiratory hypersensitivity. The identification of TRPA1 activation by toxicants from cigarette smoke and polluted air, such as crotonaldehyde, acrolein, and oxidizing agents such as hydrogen peroxide, is an important finding. These two studies enhance our understanding of how pollution and cigarette smoke can damage airway function and will hopefully pave the way for the development of rational alternative therapeutics for such airway injury. PMID:18568080

Flammability, Odor, and Offgassing Requirements and Test Procedures for Materials in Environments That Support Combustion

DTIC Science & Technology

1988-05-01

alcohol (1- octanol ) phenol n-propyl alcohol (1-propanol) isopropy1 alcohol (2-propanol) **2. Aldehydes acetaldehyde (ethanal) acrolein (propenal...59.0) D-7 MACs 7-Day ppm fmq/M^) 20 (105) 20 (82.0) 20 (70.4) 20 (70.4) Mol. Wt. methyl hexyl ketone (2- octanone ) 128.2 methyl

Glutathione S-transferase P protects against cyclophosphamide-induced cardiotoxicity in mice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Conklin, Daniel J., E-mail: dj.conklin@louisville.edu; Institute of Molecular Cardiology, University of Louisville, Louisville, KY 40292; Haberzettl, Petra

2015-06-01

High-dose chemotherapy regimens using cyclophosphamide (CY) are frequently associated with cardiotoxicity that could lead to myocyte damage and congestive heart failure. However, the mechanisms regulating the cardiotoxic effects of CY remain unclear. Because CY is converted to an unsaturated aldehyde acrolein, a toxic, reactive CY metabolite that induces extensive protein modification and myocardial injury, we examined the role of glutathione S-transferase P (GSTP), an acrolein-metabolizing enzyme, in CY cardiotoxicity in wild-type (WT) and GSTP-null mice. Treatment with CY (100–300 mg/kg) increased plasma levels of creatine kinase-MB isoform (CK·MB) and heart-to-body weight ratio to a significantly greater extent in GSTP-null thanmore » WT mice. In addition to modest yet significant echocardiographic changes following acute CY-treatment, GSTP insufficiency was associated with greater phosphorylation of c-Jun and p38 as well as greater accumulation of albumin and protein–acrolein adducts in the heart. Mass spectrometric analysis revealed likely prominent modification of albumin, kallikrein-1-related peptidase, myoglobin and transgelin-2 by acrolein in the hearts of CY-treated mice. Treatment with acrolein (low dose, 1–5 mg/kg) also led to increased heart-to-body weight ratio and myocardial contractility changes. Acrolein induced similar hypotension in GSTP-null and WT mice. GSTP-null mice also were more susceptible than WT mice to mortality associated with high-dose acrolein (10–20 mg/kg). Collectively, these results suggest that CY cardiotoxicity is regulated, in part, by GSTP, which prevents CY toxicity by detoxifying acrolein. Thus, humans with low cardiac GSTP levels or polymorphic forms of GSTP with low acrolein-metabolizing capacity may be more sensitive to CY toxicity. - Graphical abstract: Cyclophosphamide (CY) treatment results in P450-mediated metabolic formation of phosphoramide mustard and acrolein (3-propenal). Acrolein is either metabolized and detoxified by glutathione S-transferase P (GSTP) via conjugation with GSH or acrolein can react with circulating and cardiac proteins to form protein–acrolein adducts that may contribute to cardiac injury, increased vascular permeability and edema and acute cardiotoxicity. Under low dose exposure, this event is reversible but at high levels of CY treatment and/or in susceptible individuals (e.g., hGSTP1 polymorphism), CY-induced cardiotoxicity is augmented and sudden death may occur. - Highlights: • Acute cardiotoxicity of cyclophosphamide (CY) is exacerbated in GSTP-null mice. • CY altered cardiac contractility, vascular leak and protein–acrolein adducts. • Cardiotoxicity of CY is recapitulated by acrolein only exposure. • Acrolein-induced cardiotoxicity and mortality is enhanced in male GSTP-null mice.« less

Aldehyde Detection in Electronic Cigarette Aerosols

PubMed Central

2017-01-01

Acetaldehyde, acrolein, and formaldehyde are the principal toxic aldehydes present in cigarette smoke and contribute to the risk of cardiovascular disease and noncancerous pulmonary disease. The rapid growth of the use of electronic cigarettes (e-cigarettes) has raised concerns over emissions of these harmful aldehydes. This work determines emissions of these aldehydes in both free and bound (aldehyde–hemiacetal) forms and other carbonyls from the use of e-cigarettes. A novel silicon microreactor with a coating phase of 4-(2-aminooxyethyl)-morpholin-4-ium chloride (AMAH) was used to trap carbonyl compounds in the aerosols of e-cigarettes via oximation reactions. AMAH–aldehyde adducts were measured using gas chromatography–mass spectrometry. 1H nuclear magnetic resonance spectroscopy was used to analyze hemiacetals in the aerosols. These aldehydes were detected in the aerosols of all e-cigarettes. Newer-generation e-cigarette devices generated more aldehydes than the first-generation e-cigarettes because of higher battery power output. Formaldehyde–hemiacetal was detected in the aerosols generated from some e-liquids using the newer e-cigarette devices at a battery power output of 11.7 W and above. The emission of these aldehydes from all e-cigarettes, especially higher levels of aldehydes from the newer-generation e-cigarette devices, indicates the risk of using e-cigarettes. PMID:28393137

Air pollution source apportionment before, during, and after the 2008 Beijing Olympics and association of sources to aldehydes and biomarkers of blood coagulation, pulmonary and systemic inflammation, and oxidative stress in healthy young adults

NASA Astrophysics Data System (ADS)

Altemose, Brent A.

Based on principal component analysis (PCA) of air pollution data collected during the Summer Olympic Games held in Beijing, China during 2008, the five source types of air pollution identified -- natural soil/road dust, vehicle and industrial combustion, vegetative burning, oil combustion, and secondary formation, were all distinctly lower during the Olympics. This was particularly true for vehicle and industrial combustion and oil combustion, and during the main games period between the opening and closing ceremonies. The reduction in secondary formation was reflective of a reduction in nitrogen oxides, but this also contributed to increased ozone concentrations during the Olympic period. Among three toxic aldehydes measured in Beijing during the same time period, only acetaldehyde had a reduction in mean concentration during the Olympic air pollution control period compared to the pre-Olympic period. Accordingly, acetaldehyde was significantly correlated with primary emission sources including vegetative burning and oil combustion, and with several pollutants emitted mainly from primary sources. In contrast, formaldehyde and acrolein increased during the Olympic air pollution control period; accordingly both were significantly correlated with ozone and with the secondary formation source type. These findings indicate primary sources may dominate for acetaldehyde while secondary sources may dominate for formaldehyde and acrolein. Biomarkers for pulmonary inflammation (exhaled breath condensate (EBC) pH, exhaled nitric oxide, and EBC nitrite) and hemostasis and blood coagulation (vWF and sCD62p) were most consistently associated with vehicle and industrial combustion, oil combustion, and vegetative burning. The systemic inflammation biomarker 8-OHdG was most consistently associated with vehicle and industrial combustion. In contrast, the associations between the biomarkers and the aldehydes were generally not significant or in the hypothesized direction, although EBC nitrite was associated with both acrolein and acetaldehyde, and sCD62p was associated with acetaldehyde. Notably, the biomarker sCD40L showed few significant associations with any of the air pollution source types or aldehydes. The findings indicate that implementing controls for combustion sources may have a positive impact on cardiorespiratory health, even in healthy young adults. More aggressive control of vegetative burning and further reduction of nitrogen oxide concentrations would likely have an even more positive impact.

Alcohol, Aldehydes, Adducts and Airways

PubMed Central

Sapkota, Muna; Wyatt, Todd A.

2015-01-01

Drinking alcohol and smoking cigarettes results in the formation of reactive aldehydes in the lung, which are capable of forming adducts with several proteins and DNA. Acetaldehyde and malondialdehyde are the major aldehydes generated in high levels in the lung of subjects with alcohol use disorder who smoke cigarettes. In addition to the above aldehydes, several other aldehydes like 4-hydroxynonenal, formaldehyde and acrolein are also detected in the lung due to exposure to toxic gases, vapors and chemicals. These aldehydes react with nucleophilic targets in cells such as DNA, lipids and proteins to form both stable and unstable adducts. This adduction may disturb cellular functions as well as damage proteins, nucleic acids and lipids. Among several adducts formed in the lung, malondialdehyde DNA (MDA-DNA) adduct and hybrid malondialdehyde-acetaldehyde (MAA) protein adducts have been shown to initiate several pathological conditions in the lung. MDA-DNA adducts are pre-mutagenic in mammalian cells and induce frame shift and base-pair substitution mutations, whereas MAA protein adducts have been shown to induce inflammation and inhibit wound healing. This review provides an insight into different reactive aldehyde adducts and their role in the pathogenesis of lung disease. PMID:26556381

Kinetics of Forming Aldehydes in Frying Oils and Their Distribution in French Fries Revealed by LC-MS-Based Chemometrics.

PubMed

Wang, Lei; Csallany, A Saari; Kerr, Brian J; Shurson, Gerald C; Chen, Chi

2016-05-18

In this study, the kinetics of aldehyde formation in heated frying oils was characterized by 2-hydrazinoquinoline derivatization, liquid chromatography-mass spectrometry (LC-MS) analysis, principal component analysis (PCA), and hierarchical cluster analysis (HCA). The aldehydes contributing to time-dependent separation of heated soybean oil (HSO) in a PCA model were grouped by the HCA into three clusters (A1, A2, and B) on the basis of their kinetics and fatty acid precursors. The increases of 4-hydroxynonenal (4-HNE) and the A2-to-B ratio in HSO were well-correlated with the duration of thermal stress. Chemometric and quantitative analysis of three frying oils (soybean, corn, and canola oils) and French fry extracts further supported the associations between aldehyde profiles and fatty acid precursors and also revealed that the concentrations of pentanal, hexanal, acrolein, and the A2-to-B ratio in French fry extracts were more comparable to their values in the frying oils than other unsaturated aldehydes. All of these results suggest the roles of specific aldehydes or aldehyde clusters as novel markers of the lipid oxidation status for frying oils or fried foods.

Alcohol, Aldehydes, Adducts and Airways.

PubMed

Sapkota, Muna; Wyatt, Todd A

2015-11-05

Drinking alcohol and smoking cigarettes results in the formation of reactive aldehydes in the lung, which are capable of forming adducts with several proteins and DNA. Acetaldehyde and malondialdehyde are the major aldehydes generated in high levels in the lung of subjects with alcohol use disorder who smoke cigarettes. In addition to the above aldehydes, several other aldehydes like 4-hydroxynonenal, formaldehyde and acrolein are also detected in the lung due to exposure to toxic gases, vapors and chemicals. These aldehydes react with nucleophilic targets in cells such as DNA, lipids and proteins to form both stable and unstable adducts. This adduction may disturb cellular functions as well as damage proteins, nucleic acids and lipids. Among several adducts formed in the lung, malondialdehyde DNA (MDA-DNA) adduct and hybrid malondialdehyde-acetaldehyde (MAA) protein adducts have been shown to initiate several pathological conditions in the lung. MDA-DNA adducts are pre-mutagenic in mammalian cells and induce frame shift and base-pair substitution mutations, whereas MAA protein adducts have been shown to induce inflammation and inhibit wound healing. This review provides an insight into different reactive aldehyde adducts and their role in the pathogenesis of lung disease.

Applications of organocatalytic asymmetric synthesis to drug prototypes--dual action and selective inhibitors of n-nitric oxide synthase with activity against the 5-HT1D/1B subreceptors.

PubMed

Hanessian, Stephen; Stoffman, Eli; Mi, Xueling; Renton, Paul

2011-03-04

The scope of MacMillan's organocatalytic asymmetric conjugate addition reaction of indoles and electron-rich aromatics to α,β-unsaturated aldehydes has been extended to the use of 3-amino crotonaldehydes as substrates. The aromatics used include indoles as well as an aniline and a furan. The scope and effect of the groups on nitrogen (R, R') has also been studied. The method has been applied to the concise synthesis of an advanced precursor to S-(+)-1, a drug prototype for the treatment of migraine headaches.

Kinetics and products of the OH radical-initiated reaction of 3-methyl-2-butenal.

PubMed

Tuazon, Ernesto C; Aschmann, Sara M; Nishino, Noriko; Arey, Janet; Atkinson, Roger

2005-06-07

Kinetics and products of the gas-phase reaction of OH radicals with 3-methyl-2-butenal [(CH3)2C=CHCHO] have been investigated at room temperature and atmospheric pressure of air. Using a relative rate method with methacrolein as the reference compound, a rate constant for the reaction of OH radicals with 3-methyl-2-butenal of (6.21 +/- 0.18) x 10(-11) cm3 molecule(-1) s(-1) at 296 +/- 2 K was measured, where the indicated error does not include the uncertainty in the rate constant for the methacrolein reference compound. Products of this reaction were investigated using in situ Fourier transform infrared (FT-IR) spectroscopy and solid phase microextraction (SPME) fibers coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for on-fiber derivatization of carbonyl compounds, with subsequent thermal desorption and analysis by gas chromatography. The products observed and the molar formation yields were: glyoxal, 40 +/- 3%; acetone, 74 +/- 6%; 2-hydroxy-2-methylpropanal, 4.6 +/- 0.7%; CO2, 39% initially, decreasing to 30% at greater extents of reaction; peroxyacyl nitrate(s) [RC(O)OONO2], 5-8%, increasing with the extent of reaction and with the sum of the CO2 and RC(O)OONO2 yields being 38 +/- 6%; and organic nitrates [RONO2], 8.5 +/- 2.3%. The formation of these products is readily explained by a reaction mechanism based on those previously formulated for the corresponding reactions of the alpha,beta-unsaturated aldehydes acrolein, crotonaldehyde and methacrolein. Based on the mechanism proposed, at room temperature H-atom abstraction from the CHO group accounts for 40 +/- 6% of the overall reaction, and OH radical addition to the carbon atoms of the C=C bond accounts for 53 +/- 4% of the overall reaction. Hence 93 +/- 8% of the reaction products and pathways are accounted for.

Products of ozone-initiated chemistry in a simulated aircraft environment.

PubMed

Wisthaler, Armin; Tamás, Gyöngyi; Wyon, David P; Strøm-Tejsen, Peter; Space, David; Beauchamp, Jonathan; Hansel, Armin; Märk, Tilmann D; Weschler, Charles J

2005-07-01

We used proton-transfer-reaction mass spectrometry (PTR-MS) to examine the products formed when ozone reacted with the materials in a simulated aircraft cabin, including a loaded high-efficiency particulate air (HEPA) filter in the return air system. Four conditions were examined: cabin (baseline), cabin plus ozone, cabin plus soiled T-shirts (surrogates for human occupants), and cabin plus soiled T-shirts plus ozone. The addition of ozone to the cabin without T-shirts, at concentrations typically encountered during commercial air travel, increased the mixing ratio (v:v concentration) of detected pollutants from 35 ppb to 80 ppb. Most of this increase was due to the production of saturated and unsaturated aldehydes and tentatively identified low-molecular-weight carboxylic acids. The addition of soiled T-shirts, with no ozone present, increased the mixing ratio of pollutants in the cabin air only slightly, whereas the combination of soiled T-shirts and ozone increased the mixing ratio of detected pollutants to 110 ppb, with more than 20 ppb originating from squalene oxidation products (acetone, 4-oxopentanal, and 6-methyl-5-hepten-2-one). For the two conditions with ozone present, the more-abundant oxidation products included acetone/propanal (8-20 ppb), formaldehyde (8-10 ppb), nonanal (approximately 6 ppb), 4-oxopentanal (3-7 ppb), acetic acid (approximately 7 ppb), formic acid (approximately 3 ppb), and 6-methyl-5-hepten-2-one (0.5-2.5 ppb), as well as compounds tentatively identified as acrolein (0.6-1 ppb) and crotonaldehyde (0.6-0.8 ppb). The odor thresholds of certain products were exceeded. With an outdoor air exchange of 3 h(-1) and a recirculation rate of 20 h(-1), the measured ozone surface removal rate constant was 6.3 h(-1) when T-shirts were not present, compared to 11.4 h(-1) when T-shirts were present.

Acrolein generation stimulates hypercontraction in isolated human blood vessels

PubMed Central

Conklin, D.J.; Bhatnagar, A.; Cowley, H.R.; Johnson, G.H.; Wiechmann, R.J.; Sayre, L.M.; Trent, M.B.; Boor, P.J.

2012-01-01

Increased risk of vasospasm, a spontaneous hyperconstriction, is associated with atherosclerosis, cigarette smoking, and hypertension—all conditions involving oxidative stress, lipid peroxidation, and inflammation. To test the role of the lipid peroxidation- and inflammation-derived aldehyde, acrolein, in human vasospasm, we developed an ex vivo model using human coronary artery bypass graft (CABG) blood vessels and a demonstrated acrolein precursor, allylamine. Allylamine induces hypercontraction in isolated rat coronary artery in a semicarbazide-sensitive amine oxidase activity (SSAO) dependent manner. Isolated human CABG blood vessels (internal mammary artery, radial artery, saphenous vein) were used to determine: (1) vessel responses and sensitivity to acrolein, allylamine, and H2O2 exposure (1 μM–1 mM), (2) SSAO dependence of allylamine-induced effects using SSAO inhibitors (semicarbazide, 1 mM; MDL 72274-E, active isomer; MDL 72274-Z, inactive isomer; 100 μM), (3) the vasoactive effects of two other SSAO amine substrates, benzylamine and methylamine, and (4) the contribution of extracellular Ca2+ to hypercontraction. Acrolein or allylamine but not H2O2, benzylamine, or methylamine stimulated spontaneous and pharmacologically intractable hypercontraction in CABG blood vessels that was similar to clinical vasospasm. Allylamine-induced hypercontraction and blood vessel SSAO activity were abolished by pretreatment with semicarbazide or MDL 72274-E but not by MDL 72274-Z. Allylamine-induced hypercontraction also was significantly attenuated in Ca2+-free buffer. In isolated aorta of spontaneously hypertensive rat, allylamine-induced an SSAO-dependent contraction and enhanced norepinephrine sensitivity but not in Sprague–Dawley rat aorta. We conclude that acrolein generation in the blood vessel wall increases human susceptibility to vasospasm, an event that is enhanced in hypertension. PMID:17095030

Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection–absorption spectroscopy and temperature programmed desorption study

PubMed Central

Dostert, Karl-Heinz; O'Brien, Casey P.; Mirabella, Francesca; Ivars-Barceló, Francisco

2016-01-01

Atomistic-level understanding of the interaction of α,β-unsaturated aldehydes and their derivatives with late transition metals is of fundamental importance for the rational design of new catalytic materials with the desired selectivity towards C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 C vs. CO bond partial hydrogenation. In this study, we investigate the interaction of acrolein, and its partial hydrogenation products propanal and allyl alcohol, with Pd(111) as a prototypical system. A combination of infrared reflection–absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) experiments was applied under well-defined ultrahigh vacuum (UHV) conditions to obtain detailed information on the adsorption geometries of acrolein, propanal, and allyl alcohol as a function of coverage. We compare the IR spectra obtained for multilayer coverages, reflecting the molecular structure of unperturbed molecules, with the spectra acquired for sub-monolayer coverages, at which the chemical bonds of the molecules are strongly distorted. Coverage-dependent IR spectra of acrolein on Pd(111) point to the strong changes in the adsorption geometry with increasing acrolein coverage. Acrolein adsorbs with the CC and CO bonds lying parallel to the surface in the low coverage regime and changes its geometry to a more upright orientation with increasing coverage. TPD studies indicate decomposition of the species adsorbed in the sub-monolayer regime upon heating. Similar strong coverage dependence of the IR spectra were found for propanal and allyl alcohol. For all investigated molecules a detailed assignment of vibrational bands is reported. PMID:27149902

Stereospecific Formation of Interstrand Carbinolamine DNA Crosslinks by Crotonaldehyde- and Acetaldehyde-Derived α-CH3-γ-OH-1,N2-Propano-2’-deoxyguanosine Adducts in the 5′-CpG-3′ Sequence

PubMed Central

Cho, Young-Jin; Wang, Hao; Kozekov, Ivan D.; Kurtz, Andrew J.; Jacob, Jaison; Voehler, Markus; Smith, Jarrod; Harris, Thomas M.; Lloyd, R. Stephen; Rizzo, Carmelo J.; Stone, Michael P.

2008-01-01

The crotonaldehyde- and acetaldehyde-derived R- and S-α-CH3-γ-OH-1,N2-propanodeoxyguanosine adducts were monitored in single-stranded and duplex oligodeoxynucleotides using NMR spectroscopy. In both instances the cis and trans diastereomers of the α-CH3 and γ-OH groups underwent slow exchange, with the trans diastereomers being favored. In single-stranded oligodeoxynucleotides, the aldehyde intermediates were not detected spectroscopically, but their presence was revealed through the formation of N-terminal conjugates with the tetrapeptide KWKK. When annealed into 5′-d(GCTAGCXAGTCC)-3′•5′-d(GGACTCYCTAGC)-3′ containing the 5′-CpG-3′ sequence context (X=R- or S-α-CH3-γ-13C-OH-PdG; Y=15N2-dG), at pH 7, partial opening of the R- or S-α-CH3-γ-13C-OH-PdG adducts to the corresponding N2-(3-oxo-1-methyl-propyl)-dG aldehydes was observed at temperatures below the Tm of the duplexes. These aldehydes equilibrated with their geminal diol hydrates; higher temperatures favored the aldehydes. When annealed opposite to T, the S-α-CH3-γ-13C-OH-PdG adduct was stable. At 37 °C, an interstrand DNA crosslink was observed spectroscopically only for the R-α-CH3-γ-OH-PdG adduct. Molecular modeling predicted that the interstrand crosslink formed by the R-α-CH3-γ-OH-PdG adduct introduced less disruption into the duplex structure than did the crosslink arising from the S-α-CH3-γ-OH-PdG adduct, due to differing orientations of the R- and S-CH3 groups. Modeling also predicted that the α-methyl group of the aldehyde arising from the R-α-CH3-γ-OH-PdG adduct oriented in the 3′ direction in the minor groove, facilitating crosslinking. In contrast, the α-methyl group of the aldehyde arising from the S-α-CH3-γ-OH-PdG adduct oriented in the 5′ direction within the minor groove potentially hindering crosslinking. NMR revealed that for the R-α-CH3-γ-OH-PdG adduct, the carbinolamine form of the crosslink was favored in duplex DNA, in situ, with the imine or Schiff base form of the crosslink remaining below the level of spectroscopic detection. Molecular modeling predicted that the carbinolamine linkage maintained Watson-Crick hydrogen bonding at both of the tandem C•G base pairs. Dehydration of the carbinolamine crosslink to an imine, or cyclization of the latter to form a pyrimidopurinone crosslink, required disruption of Watson-Crick hydrogen bonding at one or both of the crosslinked base pairs. PMID:16485895

Aldehyde Oxidase 4 Plays a Critical Role in Delaying Silique Senescence by Catalyzing Aldehyde Detoxification.

PubMed

Srivastava, Sudhakar; Brychkova, Galina; Yarmolinsky, Dmitry; Soltabayeva, Aigerim; Samani, Talya; Sagi, Moshe

2017-04-01

The Arabidopsis ( Arabidopsis thaliana ) aldehyde oxidases are a multigene family of four oxidases (AAO1-AAO4) that oxidize a variety of aldehydes, among them abscisic aldehyde, which is oxidized to the phytohormone abscisic acid. Toxic aldehydes are generated in plants both under normal conditions and in response to stress. The detoxification of such aldehydes by oxidation is attributed to aldehyde dehydrogenases but never to aldehyde oxidases. The feasibility of the detoxification of aldehydes in siliques via oxidation by AAO4 was demonstrated, first, by its ability to efficiently oxidize an array of aromatic and aliphatic aldehydes, including the reactive carbonyl species (RCS) acrolein, hydroxyl-2-nonenal, and malondialdehyde. Next, exogenous application of several aldehydes to siliques in AAO4 knockout (KO) Arabidopsis plants induced severe tissue damage and enhanced malondialdehyde levels and senescence symptoms, but not in wild-type siliques. Furthermore, abiotic stresses such as dark and ultraviolet C irradiation caused an increase in endogenous RCS and higher expression levels of senescence marker genes, leading to premature senescence of KO siliques, whereas RCS and senescence marker levels in wild-type siliques were hardly affected. Finally, in naturally senesced KO siliques, higher endogenous RCS levels were associated with enhanced senescence molecular markers, chlorophyll degradation, and earlier seed shattering compared with the wild type. The aldehyde-dependent differential generation of superoxide and hydrogen peroxide by AAO4 and the induction of AAO4 expression by hydrogen peroxide shown here suggest a self-amplification mechanism for detoxifying additional reactive aldehydes produced during stress. Taken together, our results indicate that AAO4 plays a critical role in delaying senescence in siliques by catalyzing aldehyde detoxification. © 2017 American Society of Plant Biologists. All Rights Reserved.

Aldehyde Oxidase 4 Plays a Critical Role in Delaying Silique Senescence by Catalyzing Aldehyde Detoxification1[OPEN

PubMed Central

Yarmolinsky, Dmitry; Soltabayeva, Aigerim; Samani, Talya

2017-01-01

The Arabidopsis (Arabidopsis thaliana) aldehyde oxidases are a multigene family of four oxidases (AAO1–AAO4) that oxidize a variety of aldehydes, among them abscisic aldehyde, which is oxidized to the phytohormone abscisic acid. Toxic aldehydes are generated in plants both under normal conditions and in response to stress. The detoxification of such aldehydes by oxidation is attributed to aldehyde dehydrogenases but never to aldehyde oxidases. The feasibility of the detoxification of aldehydes in siliques via oxidation by AAO4 was demonstrated, first, by its ability to efficiently oxidize an array of aromatic and aliphatic aldehydes, including the reactive carbonyl species (RCS) acrolein, hydroxyl-2-nonenal, and malondialdehyde. Next, exogenous application of several aldehydes to siliques in AAO4 knockout (KO) Arabidopsis plants induced severe tissue damage and enhanced malondialdehyde levels and senescence symptoms, but not in wild-type siliques. Furthermore, abiotic stresses such as dark and ultraviolet C irradiation caused an increase in endogenous RCS and higher expression levels of senescence marker genes, leading to premature senescence of KO siliques, whereas RCS and senescence marker levels in wild-type siliques were hardly affected. Finally, in naturally senesced KO siliques, higher endogenous RCS levels were associated with enhanced senescence molecular markers, chlorophyll degradation, and earlier seed shattering compared with the wild type. The aldehyde-dependent differential generation of superoxide and hydrogen peroxide by AAO4 and the induction of AAO4 expression by hydrogen peroxide shown here suggest a self-amplification mechanism for detoxifying additional reactive aldehydes produced during stress. Taken together, our results indicate that AAO4 plays a critical role in delaying senescence in siliques by catalyzing aldehyde detoxification. PMID:28188272

Comparison and characterization of volatile compounds as markers of oils stability during frying by HS-SPME-GC/MS and Chemometric analysis.

PubMed

Ben Hammouda, Ibtissem; Freitas, Flavia; Ammar, Sonda; Da Silva, M D R Gomes; Bouaziz, Mohamed

2017-11-15

The formation and emission of volatile compounds, including the aldehydes and some toxic compounds of oil samples, ROPO pure (100%) and the blended ROPO/RCO (80-20%), were carried out during deep frying at 180°C. The volatile profile of both oil samples was evaluated by an optimized HS-SPME-GC/MS method, before and after 20, 40 and 60 successive sessions of deep-frying. Actually, from 100 detected compounds, aldehydes were found to be the main group formed. In addition, the oil degradation under thermal treatment regarding the volatile compounds were evaluated and compared. Consequently, the blended ROPO/RCO revealed fewer formations of unsaturated aldehydes, including toxic ones, such as acrolein, and showed a greater stability against oxidative thermal degradation compared to ROPO pure. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparative study of glass tube and mist chamber sampling techniques for the analysis of gaseous carbonyl compounds

NASA Astrophysics Data System (ADS)

François, Stéphanie; Perraud, Véronique; Pflieger, Maryline; Monod, Anne; Wortham, Henri

In this work, glass tube and mist chamber sampling techniques using 2,4-dinitrophenylhydrazine as derivative agent for the analysis of gaseous carbonyl compounds are compared. Trapping efficiencies of formaldehyde, acetaldehyde, propionaldehyde, acetone, acrolein, glyoxal, crotonaldehyde, benzaldehyde, butyraldehyde and valeraldehyde are experimentally determined using a gas-phase generator. In addition to generalise our results to all atmospheric gaseous compounds and derivative agents, theoretical trapping efficiencies and enrichment factors are expressed taking into account mechanisms involved in the two kinds of traps. Theoretical and experimental results show that, as expected, the trapping efficiencies of the glass tube depend mainly on solubility of compounds. The results provide new information and better understanding of phenomena occurring in the mist chamber and the ability of this sampler to concentrate the samples. Hence, the mist chamber is the more convenient sampling method when the trapping is associated to a fast derivatisation of the compounds and the glass tube technique must be used to trap atmospheric compounds without simultaneous derivatisation.

Formation mechanism of glyoxal-DNA adduct, a DNA cross-link precursor.

PubMed

Vilanova, B; Fernández, D; Casasnovas, R; Pomar, A M; Alvarez-Idaboy, J R; Hernández-Haro, N; Grand, A; Adrover, M; Donoso, J; Frau, J; Muñoz, F; Ortega-Castro, J

2017-05-01

DNA nucleobases undergo non-enzymatic glycation to nucleobase adducts which can play important roles in vivo. In this work, we conducted a comprehensive experimental and theoretical kinetic study of the mechanisms of formation of glyoxal-guanine adducts over a wide pH range in order to elucidate the molecular basis for the glycation process. Also, we performed molecular dynamics simulations to investigate how open or cyclic glyoxal-guanine adducts can cause structural changes in an oligonucleotide model. A thermodynamic study of other glycating agents including methylglyoxal, acrolein, crotonaldehyde, 4-hydroxynonenal and 3-deoxyglucosone revealed that, at neutral pH, cyclic adducts were more stable than open adducts; at basic pH, however, the open adducts of 3-deoxyglucosone, methylglyoxal and glyoxal were more stable than their cyclic counterparts. This result can be ascribed to the ability of the adducts to cross-link DNA. The new insights may contribute to improve our understanding of the connection between glycation and DNA cross-linking. Copyright © 2017 Elsevier B.V. All rights reserved.

Regulation of NF-κB-Induced Inflammatory Signaling by Lipid Peroxidation-Derived Aldehydes

PubMed Central

Yadav, Umesh C. S.; Ramana, Kota V.

2013-01-01

Oxidative stress plays a critical role in the pathophysiology of a wide range of diseases including cancer. This view has broadened significantly with the recent discoveries that reactive oxygen species initiated lipid peroxidation leads to the formation of potentially toxic lipid aldehyde species such as 4-hydroxy-trans-2-nonenal (HNE), acrolein, and malondialdehyde which activate various signaling intermediates that regulate cellular activity and dysfunction via a process called redox signaling. The lipid aldehyde species formed during synchronized enzymatic pathways result in the posttranslational modification of proteins and DNA leading to cytotoxicity and genotoxicty. Among the lipid aldehyde species, HNE has been widely accepted as a most toxic and abundant lipid aldehyde generated during lipid peroxidation. HNE and its glutathione conjugates have been shown to regulate redox-sensitive transcription factors such as NF-κB and AP-1 via signaling through various protein kinase cascades. Activation of redox-sensitive transcription factors and their nuclear localization leads to transcriptional induction of several genes responsible for cell survival, differentiation, and death. In this review, we describe the mechanisms by which the lipid aldehydes transduce activation of NF-κB signaling pathways that may help to develop therapeutic strategies for the prevention of a number of inflammatory diseases. PMID:23710287

Field validation of the dnph method for aldehydes and ketones. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Workman, G.S.; Steger, J.L.

1996-04-01

A stationary source emission test method for selected aldehydes and ketones has been validated. The method employs a sampling train with impingers containing 2,4-dinitrophenylhydrazine (DNPH) to derivatize the analytes. The resulting hydrazones are recovered and analyzed by high performance liquid chromatography. Nine analytes were studied; the method was validated for formaldehyde, acetaldehyde, propionaldehyde, acetophenone and isophorone. Acrolein, menthyl ethyl ketone, menthyl isobutyl ketone, and quinone did not meet the validation criteria. The study employed the validation techniques described in EPA method 301, which uses train spiking to determine bias, and collocated sampling trains to determine precision. The studies were carriedmore » out at a plywood veneer dryer and a polyester manufacturing plant.« less

Polyacrolein microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor)

1983-01-01

Microspheres of acrolein homopolymers and co-polymer with hydrophillic comonomers such as methacrylic acid and/or hydroxyethylmethacrylate are prepared by cobalt gamma irradiation of dilute aqueous solutions of the monomers in presence of suspending agents, especially alkyl sulfates such as sodium dodecyl sulfate. Amine or hydroxyl modification is achieved by forming adducts with diamines or alkanol amines. Carboxyl modification is effected by oxidation with peroxides. Pharmaceuticals or other aldehyde reactive materials can be coupled to the microspheres. The microspheres directly form antibody adducts without agglomeration.

Polyacrolein microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor)

1986-01-01

Microspheres of acrolein homopolymers and copolymer with hydrophillic comonomers such as methacrylic acid and/or hydroxyethylmethacrylate are prepared by cobalt gamma irradiation of dilute aqueous solutions of the monomers in presence of suspending agents, especially alkyl sulfates such as sodium dodecyl sulfate. Amine or hydroxyl modification is achieved by forming adducts with diamines or alkanol amines. Carboxyl modification is effected by oxidation with peroxides. Pharmaceuticals or other aldehyde reactive materials can be coupled to the microspheres. The microspheres directly form antibody adducts without agglomeration.

Polyacrolein microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor)

1987-01-01

Microspheres of acrolein homopolymers and copolymer with hydrophillic comonomers such as methacrylic acid and/or hydroxyethylmethacrylate are prepared by cobalt gamma irradiation of dilute aqueous solutions of the monomers in presence of suspending agents, especially alkyl sulfates such as sodium dodecyl sulfate. Amine or hydroxyl modification is achieved by forming adducts with diamines or alkanol amines. Carboxyl modification is effected by oxidation with peroxides. Pharmaceuticals or other aldehyde reactive materials can be coupled to the microspheres. The microspheres directly form antibody adducts without agglomeration.

An integrated QSAR-PBK/D modelling approach for predicting detoxification and DNA adduct formation of 18 acyclic food-borne α,β-unsaturated aldehydes.

PubMed

Kiwamoto, R; Spenkelink, A; Rietjens, I M C M; Punt, A

2015-01-01

Acyclic α,β-unsaturated aldehydes present in food raise a concern because the α,β-unsaturated aldehyde moiety is considered a structural alert for genotoxicity. However, controversy remains on whether in vivo at realistic dietary exposure DNA adduct formation is significant. The aim of the present study was to develop physiologically based kinetic/dynamic (PBK/D) models to examine dose-dependent detoxification and DNA adduct formation of a group of 18 food-borne acyclic α,β-unsaturated aldehydes without 2- or 3-alkylation, and with no more than one conjugated double bond. Parameters for the PBK/D models were obtained using quantitative structure-activity relationships (QSARs) defined with a training set of six selected aldehydes. Using the QSARs, PBK/D models for the other 12 aldehydes were defined. Results revealed that DNA adduct formation in the liver increases with decreasing bulkiness of the molecule especially due to less efficient detoxification. 2-Propenal (acrolein) was identified to induce the highest DNA adduct levels. At realistic dietary intake, the predicted DNA adduct levels for all aldehydes were two orders of magnitude lower than endogenous background levels observed in disease free human liver, suggesting that for all 18 aldehydes DNA adduct formation is negligible at the relevant levels of dietary intake. The present study provides a proof of principle for the use of QSAR-based PBK/D modelling to facilitate group evaluations and read-across in risk assessment. Copyright © 2014 Elsevier Inc. All rights reserved.

Reactive Secondary Sequence Oxidative Pathology Polymer Model and Antioxidant Tests

PubMed Central

Petersen, Richard C.

2014-01-01

Aims To provide common Organic Chemistry/Polymer Science thermoset free-radical crosslinking Sciences for Medical understanding and also present research findings for several common vitamins/antioxidants with a new class of drugs known as free-radical inhibitors. Study Design Peroxide/Fenton transition-metal redox couples that generate free radicals were combined with unsaturated lipid oils to demonstrate thermoset-polymer chain growth by crosslinking with the α-β-unsaturated aldehyde acrolein into rubbery/adhesive solids. Further, Vitamin A and beta carotene were similarly studied for crosslink pathological potential. Also, free-radical inhibitor hydroquinone was compared for antioxidant capability with Vitamin E. Place and Duration of Study Department of Materials Science and Engineering and Department of Biomaterials, University of Alabama at Birmingham, between June 2005 and August 2012. Methodology Observations were recorded for Fenton free-radical crosslinking of unsaturated lipids and vitamin A/beta carotene by photography further with weight measurements and percent-shrinkage testing directly related to covalent crosslinking of unsaturated lipids recorded over time with different concentrations of acrolein. Also, hydroquinone and vitamin E were compared at concentrations from 0.0–7.3wt% as antioxidants for reductions in percent-shrinkage measurements, n = 5. Results Unsaturated lipid oils responded to Fenton thermoset-polymer reactive secondary sequence reactions only by acrolein with crosslinking into rubbery-type solids and different non-solid gluey products. Further, molecular oxygen crosslinking was demonstrated with lipid peroxidation and acrolein at specially identified margins. By peroxide/Fenton free-radical testing, both vitamin A and beta-carotene demonstrated possible pathology chemistry for chain-growth crosslinking. During lipid/acrolein testing over a 50 hour time period at 7.3wt% antioxidants, hydroquinone significantly reduced percent shrinkage greatly compared to the standard antioxidant vitamin E, %shrinkage at 11.6 ±1.3 for hydroquinone and 27.8 ±2.2 for vitamin E, P = .001. Conclusion Free radicals crosslinked unsaturated lipid fatty acids into thermoset polymers through Fenton reactions when combined with acrolein. Further, hydroquinone was a superior antioxidant to vitamin E. PMID:25909053

The Involvement of Lipid Peroxide-Derived Aldehydes in Aluminum Toxicity of Tobacco Roots1[W][OA

PubMed Central

Yin, Lina; Mano, Jun'ichi; Wang, Shiwen; Tsuji, Wataru; Tanaka, Kiyoshi

2010-01-01

Oxidative injury of the root elongation zone is a primary event in aluminum (Al) toxicity in plants, but the injuring species remain unidentified. We verified the hypothesis that lipid peroxide-derived aldehydes, especially highly electrophilic α,β-unsaturated aldehydes (2-alkenals), participate in Al toxicity. Transgenic tobacco (Nicotiana tabacum) overexpressing Arabidopsis (Arabidopsis thaliana) 2-alkenal reductase (AER-OE plants), wild-type SR1, and an empty vector-transformed control line (SR-Vec) were exposed to AlCl3 on their roots. Compared with the two controls, AER-OE plants suffered less retardation of root elongation under AlCl3 treatment and showed more rapid regrowth of roots upon Al removal. Under AlCl3 treatment, the roots of AER-OE plants accumulated Al and H2O2 to the same levels as did the sensitive controls, while they accumulated lower levels of aldehydes and suffered less cell death than SR1 and SR-Vec roots. In SR1 roots, AlCl3 treatment markedly increased the contents of the highly reactive 2-alkenals acrolein, 4-hydroxy-(E)-2-hexenal, and 4-hydroxy-(E)-2-nonenal and other aldehydes such as malondialdehyde and formaldehyde. In AER-OE roots, accumulation of these aldehydes was significantly less. Growth of the roots exposed to 4-hydroxy-(E)-2-nonenal and (E)-2-hexenal were retarded more in SR1 than in AER-OE plants. Thus, the lipid peroxide-derived aldehydes, formed downstream of reactive oxygen species, injured root cells directly. Their suppression by AER provides a new defense mechanism against Al toxicity. PMID:20023145

Development of a test method for carbonyl compounds from stationary source emissions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhihua Fan; Peterson, M.R.; Jayanty, R.K.M.

1997-12-31

Carbonyl compounds have received increasing attention because of their important role in ground-level ozone formation. The common method used for the measurement of aldehydes and ketones is 2,4-dinitrophenylhydrazine (DNPH) derivatization followed by high performance liquid chromatography and ultra violet (HPLC-UV) analysis. One of the problems associated with this method is the low recovery for certain compounds such as acrolein. This paper presents a study in the development of a test method for the collection and measurement of carbonyl compounds from stationary source emissions. This method involves collection of carbonyl compounds in impingers, conversion of carbonyl compounds to a stable derivativemore » with O-2,3,4,5,6-pentafluorobenzyl hydroxylamine hydrochloride (PFBHA), and separation and measurement by electron capture gas chromatography (GC-ECD). Eight compounds were selected for the evaluation of this method: formaldehyde, acetaldehyde, acrolein, acetone, butanal, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and hexanal.« less

Analytical method for lipoperoxidation relevant reactive aldehydes in human sera by high-performance liquid chromatography-fluorescence detection.

PubMed

El-Maghrabey, Mahmoud H; Kishikawa, Naoya; Ohyama, Kaname; Kuroda, Naotaka

2014-11-01

A validated, simple and sensitive HPLC method was developed for the simultaneous determination of lipoperoxidation relevant reactive aldehydes: glyoxal (GO), acrolein (ACR), malondialdehyde (MDA), and 4-hydroxy-2-nonenal (HNE) in human serum. The studied aldehydes were reacted with 2,2'-furil to form fluorescent difurylimidazole derivatives that were separated on a C18 column using gradient elution and fluorescence detection at excitation and emission wavelengths of 250 and 355nm, respectively. The method showed good linearity over the concentration ranges of 0.100-5.00, 0.200-10.0, 0.200-40.0, and 0.400-10.0nmol/mL for GO, ACR, HNE, and MDA, respectively, with detection limits ranging from 0.030 to 0.11nmol/mL. The percentage RSD of intraday and interday precision did not exceed 5.0 and 6.2%, respectively, and the accuracy (%found) ranged from 95.5 to 103%. The proposed method was applied for monitoring the four aldehydes in sera of healthy, diabetic, and rheumatic human subjects with simple pretreatment steps and without interference from endogenous components. By virtue of its high sensitivity and accuracy, our method enabled detection of differences between analytes concentrations in sera of human subjects under different clinical conditions. Copyright © 2014 Elsevier Inc. All rights reserved.

Dynamic spiking studies using the DNPH sampling train

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steger, J.L.; Knoll, J.E.

1996-12-31

The proposed aldehyde and ketone sampling method using aqueous 2,4-dinitrophenylhydrazine (DNPH) was evaluated in the laboratory and in the field. The sampling trains studied were based on the train described in SW 846 Method 0011. Nine compounds were evaluated: formaldehyde, acetaldehyde, quinone, acrolein, propionaldeyde, methyl isobutyl ketone, methyl ethyl ketone, acetophenone, and isophorone. In the laboratory, the trains were spiked both statistically and dynamically. Laboratory studies also investigated potential interferences to the method. Based on their potential to hydrolyze in acid solution to form formaldehyde, dimethylolurea, saligenin, s-trioxane, hexamethylenetetramine, and paraformaldehyde were investigated. Ten runs were performed using quadruplicate samplingmore » trains. Two of the four trains were dynamically spiked with the nine aldehydes and ketones. The test results were evaluated using the EPA method 301 criteria for method precision (< + pr - 50% relative standard deviation) and bias (correction factor of 1.00 + or - 0.30).« less

An integrated QSAR-PBK/D modelling approach for predicting detoxification and DNA adduct formation of 18 acyclic food-borne α,β-unsaturated aldehydes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kiwamoto, R., E-mail: reiko.kiwamoto@wur.nl; Spenkelink, A.; Rietjens, I.M.C.M.

Acyclic α,β-unsaturated aldehydes present in food raise a concern because the α,β-unsaturated aldehyde moiety is considered a structural alert for genotoxicity. However, controversy remains on whether in vivo at realistic dietary exposure DNA adduct formation is significant. The aim of the present study was to develop physiologically based kinetic/dynamic (PBK/D) models to examine dose-dependent detoxification and DNA adduct formation of a group of 18 food-borne acyclic α,β-unsaturated aldehydes without 2- or 3-alkylation, and with no more than one conjugated double bond. Parameters for the PBK/D models were obtained using quantitative structure–activity relationships (QSARs) defined with a training set of sixmore » selected aldehydes. Using the QSARs, PBK/D models for the other 12 aldehydes were defined. Results revealed that DNA adduct formation in the liver increases with decreasing bulkiness of the molecule especially due to less efficient detoxification. 2-Propenal (acrolein) was identified to induce the highest DNA adduct levels. At realistic dietary intake, the predicted DNA adduct levels for all aldehydes were two orders of magnitude lower than endogenous background levels observed in disease free human liver, suggesting that for all 18 aldehydes DNA adduct formation is negligible at the relevant levels of dietary intake. The present study provides a proof of principle for the use of QSAR-based PBK/D modelling to facilitate group evaluations and read-across in risk assessment. - Highlights: • Physiologically based in silico models were made for 18 α,β-unsaturated aldehydes. • Kinetic parameters were determined by in vitro incubations and a QSAR approach. • DNA adduct formation was negligible at levels relevant for dietary intake. • The use of QSAR-based PBK/D modelling facilitates group evaluations and read-across.« less

Topically applied metal chelator reduces thermal injury progression in a rat model of brass comb burn.

PubMed

Wang, Cheng Z; Ayadi, Amina El; Goswamy, Juhi; Finnerty, Celeste C; Mifflin, Randy; Sousse, Linda; Enkhbaatar, Perenlei; Papaconstantinou, John; Herndon, David N; Ansari, Naseem H

2015-12-01

Oxidative stress may be involved in the cellular damage and tissue destruction as burn wounds continues to progress after abatement of the initial insult. Since iron and calcium ions play key roles in oxidative stress, this study tested whether topical application of Livionex formulation (LF) lotion, that contains disodium EDTA as a metal chelator and methyl sulfonyl methane (MSM) as a permeability enhancer, would prevent or reduce burns. We used an established brass comb burn model with some modifications. Topical application of LF lotion was started 5 min post-burn, and repeated every 8 h for 3 consecutive days. Rats were euthanized and skin harvested for histochemistry and immunohistochemistry. Formation of protein adducts of 4-hydroxynonenal (HNE), malonadialdehyde (MDA) and acrolein (ACR) and expression of aldehyde dehydrogenase (ALDH) isozymes, ALDH1 and ALDH2 were assessed. LF lotion-treated burn sites and interspaces showed mild morphological improvement compared to untreated burn sites. Furthermore, the lotion significantly decreased the immunostaining of lipid aldehyde-protein adducts including protein -HNE, -MDA and -ACR adducts, and restored the expression of aldehyde dehydrogenase isozymes in the unburned interspaces. This data, for the first time, demonstrates that a topically applied EDTA-containing lotion protects burns progression with a concomitant decrease in the accumulation of reactive lipid aldehydes and protection of aldehyde dehydrogenase isozymes. Present studies are suggestive of therapeutic intervention of burns by this novel lotion. Copyright © 2015 Elsevier Ltd and ISBI. All rights reserved.

Topically Applied Metal Chelator Reduces Thermal Injury Progression in a Rat Model of Brass Comb Burn

PubMed Central

Wang, Cheng Z.; El Ayadi, Amina; Goswamy, Juhi; Finnerty, Celeste C.; Mifflin, Randy; Sousse, Linda; Enkhbaatar, Perenlei; Papaconstantinou, John; Herndon, David N.; Ansari, Naseem H.

2016-01-01

Oxidative stress may be involved in the cellular damage and tissue destruction as burn wounds continues to progress after abatement of the initial insult. Since iron and calcium ions play key roles in oxidative stress, this study tested whether topical application of Livionex formulation (LF) lotion, that contains disodium EDTA as a metal chelator and methyl sulfonyl methane (MSM) as a permeability enhancer, would prevent or reduce burn injury. Methods We used an established brass comb burn model with some modifications. Topical application of LF lotion was started 5 minutes post-burn, and repeated every 8 hours for 3 consecutive days. Rats were euthanized and skin harvested for histochemistry and immunohistochemistry. Formation of protein adducts of 4-hydroxynonenal (HNE), malonadialdehyde (MDA) and acrolein (ACR) and expression of aldehyde dehydrogenase (ALDH) isozymes, ALDH1 and ALDH2 were assessed. Results LF lotion-treated burn sites and interspaces showed mild morphological improvement compared to untreated burn sites. Furthermore, the lotion significantly decreased the immunostaining of lipid aldehyde-protein adducts including protein -HNE, -MDA and -ACR adducts, and restored the expression of aldehyde dehydrogenase isozymes in the unburned interspaces. Conclusion This data, for the first time, demonstrates that a topically applied EDTA-containing lotion protects burn injury progression with a concomitant decrease in the accumulation of reactive lipid aldehydes and protection of aldehyde dehydrogenase isozymes. Present studies are suggestive of therapeutic intervention of burn injury by this novel lotion. PMID:26392023

Gas chromatography-mass spectrometry of carbonyl compounds in cigarette mainstream smoke after derivatization with 2,4-dinitrophenylhydrazine.

PubMed

Dong, Ji-Zhou; Moldoveanu, Serban C

2004-02-20

An improved gas chromatography-mass spectrometry (GC-MS) method was described for the analysis of carbonyl compounds in cigarette mainstream smoke (CMS) after 2,4-dinitrophenylhydrazine (DNPH) derivatization. Besides formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, methyl ethyl ketone, butyraldehyde, and crotonaldehyde that are routinely analyzed in cigarette smoke, this technique separates and allows the analysis of several C4, C5 and C6 isomeric carbonyl compounds. Differentiation could be made between the linear and branched carbon chain components. In cigarette smoke, the branched chain carbonyls are found at higher level than the linear chain carbonyls. Also, several trace carbonyl compounds such as methoxyacetaldehyde were found for the first time in cigarette smoke. For the analysis, cigarette smoke was collected using DNPH-treated pads, which is a simpler procedure compared to conventional impinger collection. Thermal decomposition of DNPH-carbonyl compounds was minimized by the optimization of the GC conditions. The linear range of the method was significantly improved by using a standard mixture of DNPH-carbonyl compounds instead of individual compounds for calibration. The minimum detectable quantity for the carbonyls ranged from 1.4 to 5.6 microg/cigarette.

Oxidative stress and human spermatozoa: diagnostic and functional significance of aldehydes generated as a result of lipid peroxidation.

PubMed

Moazamian, Ryan; Polhemus, Ashley; Connaughton, Haley; Fraser, Barbara; Whiting, Sara; Gharagozloo, Parviz; Aitken, Robert John

2015-06-01

Oxidative stress is known to compromise human sperm function and to activate the intrinsic apoptotic cascade in these cells. One of the key features of oxidatively stressed spermatozoa is the induction of a lipid peroxidation process that results in the formation of aldehydes potentially capable of disrupting sperm function through the formation of adducts with DNA and key proteins. In this study, we have examined the impact of a range of small molecular mass aldehydes generated as a consequence of lipid peroxidation on human sperm function and also compared the two most commonly formed compounds, 4-hydroxynonenal (4HNE) and malondialdehyde (MDA), for their relative ability to reflect a state of oxidative stress in these cells. Dramatic differences in the bioactivity of individual aldehydes were observed, that generally correlated with the second order rate constants describing their interaction with the model nucleophile, glutathione. Our results demonstrate that acrolein and 4HNE were the most reactive lipid aldehydes, inhibiting sperm motility while augmenting reactive oxygen species production, lipid peroxidation, oxidative DNA damage and caspase activation, in a dose-dependent manner (P < 0.001). In contrast, a variety of saturated aldehydes and the well-known marker of oxidative stress, MDA, were without effect on this cell type. While MDA was not cytotoxic per se, its generation did reflect the induction of oxidative stress in vivo and in vitro in a manner that was highly correlated with the bioactive lipid aldehyde, 4HNE. Despite such overall correlations, individual patient samples were observed in which either MDA or 4HNE predominated. Given the relative cytotoxicity of 4HNE, we propose that this aldehyde should be the preferred criterion for diagnosing oxidative stress in the male germ line. © The Author 2015. Published by Oxford University Press on behalf of the European Society of Human Reproduction and Embryology. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Electrophilic aldehyde products of lipid peroxidation selectively adduct to heat shock protein 90 and arylsulfatase A in stallion spermatozoa.

PubMed

Hall, Sally E; Aitken, R John; Nixon, Brett; Smith, Nathan D; Gibb, Zamira

2017-01-01

Oxidative stress is a major determinant of mammalian sperm function stimulating lipid peroxidation cascades that culminate in the generation of potentially cytotoxic aldehydes. The aim of this study was to assess the impact of such aldehydes on the functionality of stallion spermatozoa. The impact of exposure to exogenous acrolein (ACR) and 4-hydroxynonenal (4HNE) was manifested in a highly significant dose- and time-dependent increase in mitochondrial reactive oxygen species (ROS), total cellular ROS, a decrease in sperm motility, and a time-dependent increase in lipid peroxidation. Notably, low doses of ACR and 4HNE also caused a significant decrease in zona binding. In contrast, exogenous malondialdehyde, a commonly used marker of oxidative stress, had little impact on the various sperm parameters assessed. In accounting for the negative physiological impact of ACR and 4HNE, it was noted that both aldehydes readily adducted to sperm proteins located predominantly within the head, proximal centriole, and tail. The detoxifying activity of mitochondrial aldehyde dehydrogenase 2 appeared responsible for a lack of adduction in the midpiece; however, this activity was overwhelmed by 24 h of electrophilic aldehyde exposure. Sequencing of the dominant proteins targeted for ACR and 4HNE covalent modification identified heat shock protein 90 alpha (cytosolic) class A member 1 and arylsulfatase A, respectively. These collective findings may prove useful in the identification of diagnostic biomarkers of stallion fertility and resolving the mechanistic basis of sperm dysfunction in this species. © The Authors 2016. Published by Oxford University Press on behalf of Society for the Study of Reproduction. All rights reserved. For permissions, please journals.permissions@oup.com.

Crotonaldehyde

Integrated Risk Information System (IRIS)

Crotonaldehyde ; CASRN 123 - 73 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

Elastin aging and lipid oxidation products in human aorta.

PubMed

Zarkovic, Kamelija; Larroque-Cardoso, Pauline; Pucelle, Mélanie; Salvayre, Robert; Waeg, Georg; Nègre-Salvayre, Anne; Zarkovic, Neven

2015-01-01

Vascular aging is associated with structural and functional modifications of the arteries, and by an increase in arterial wall thickening in the intima and the media, mainly resulting from structural modifications of the extracellular matrix (ECM) components. Among the factors known to accumulate with aging, advanced lipid peroxidation end products (ALEs) are a hallmark of oxidative stress-associated diseases such as atherosclerosis. Aldehydes generated from the peroxidation of polyunsaturated fatty acids (PUFA), (4-hydroxynonenal, malondialdehyde, acrolein), form adducts on cellular proteins, leading to a progressive protein dysfunction with consequences in the pathophysiology of vascular aging. The contribution of these aldehydes to ECM modification is not known. This study was carried out to investigate whether aldehyde-adducts are detected in the intima and media in human aorta, whether their level is increased in vascular aging, and whether elastin fibers are a target of aldehyde-adduct formation. Immunohistological and confocal immunofluorescence studies indicate that 4-HNE-histidine-adducts accumulate in an age-related manner in the intima, media and adventitia layers of human aortas, and are mainly expressed in smooth muscle cells. In contrast, even if the structure of elastin fiber is strongly altered in the aged vessels, our results show that elastin is not or very poorly modified by 4-HNE. These data indicate a complex role for lipid peroxidation and in particular for 4-HNE in elastin homeostasis, in the vascular wall remodeling during aging and atherosclerosis development. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Elastin aging and lipid oxidation products in human aorta

PubMed Central

Zarkovic, Kamelija; Larroque-Cardoso, Pauline; Pucelle, Mélanie; Salvayre, Robert; Waeg, Georg; Nègre-Salvayre, Anne; Zarkovic, Neven

2014-01-01

Vascular aging is associated with structural and functional modifications of the arteries, and by an increase in arterial wall thickening in the intima and the media, mainly resulting from structural modifications of the extracellular matrix (ECM) components. Among the factors known to accumulate with aging, advanced lipid peroxidation end products (ALEs) are a hallmark of oxidative stress-associated diseases such as atherosclerosis. Aldehydes generated from the peroxidation of polyunsaturated fatty acids (PUFA), (4-hydroxynonenal, malondialdehyde, acrolein), form adducts on cellular proteins, leading to a progressive protein dysfunction with consequences in the pathophysiology of vascular aging. The contribution of these aldehydes to ECM modification is not known. This study was carried out to investigate whether aldehyde-adducts are detected in the intima and media in human aorta, whether their level is increased in vascular aging, and whether elastin fibers are a target of aldehyde-adduct formation. Immunohistological and confocal immunofluorescence studies indicate that 4-HNE-histidine-adducts accumulate in an age-related manner in the intima, media and adventitia layers of human aortas, and are mainly expressed in smooth muscle cells. In contrast, even if the structure of elastin fiber is strongly altered in the aged vessels, our results show that elastin is not or very poorly modified by 4-HNE. These data indicate a complex role for lipid peroxidation and in particular for 4-HNE in elastin homeostasis, in the vascular wall remodeling during aging and atherosclerosis development. PMID:25553420

Mass Spectrometric Approaches to the Identification of Potential Ingredients in Cigarette Smoke Causing Cytotoxicity.

PubMed

Horiyama, Shizuyo; Kunitomo, Masaru; Yoshikawa, Noriko; Nakamura, Kazuki

2016-01-01

Cigarette smoke contains many harmful chemicals that contribute to the pathogenesis of smoking-related diseases such as chronic obstructive pulmonary disease, cancer, and cardiovascular disease. Many studies have been done to identify cytotoxic chemicals in cigarette smoke and elucidate the onset of the above-mentioned diseases caused by smoking. However, definitive mechanisms for cigarette smoke toxicity remain unknown. As candidates for cytotoxic chemicals, we have recently found methyl vinyl ketone (MVK) and acetic anhydride in nicotine/tar-free cigarette smoke extract (CSE) using L-tyrosine (Tyr), an amino acid with highly reactive hydroxyl group. The presence of MVK and acetic anhydride in CSE was confirmed by gas chromatography-mass spectrometry (GC/MS). We also found new reaction products formed in B16-BL6 mouse melanoma (B16-BL6) cells treated with CSE using LC/MS. These were identified as glutathione (GSH) conjugates of α,β-unsaturated carbonyl compounds, MVK, crotonaldehyde (CA), and acrolein (ACR), by the mass value and product ion spectra of these new products. ACR and MVK are type-2 alkenes, which are well known as electron acceptors and form Michael-type adducts to nucleophilic side chain of amino acids on peptides. These α,β-unsaturated carbonyl compounds may have a key role in CSE-induced cell death.

Accumulation of electrophilic aldehydes during postovulatory aging of mouse oocytes causes reduced fertility, oxidative stress, and apoptosis.

PubMed

Lord, Tessa; Martin, Jacinta H; Aitken, R John

2015-02-01

With increasing periods of time following ovulation, the metaphase II (MII)-stage oocyte experiences overproduction of reactive oxygen species and elevated levels of lipid peroxidation that are implicitly linked with functional deficiencies acquired during postovulatory oocyte aging. We have demonstrated that the electrophilic aldehydes 4-hydroxynonenal (4HNE), malondialdehyde, and acrolein are by-products of nonenzymatic lipid peroxidation in the murine MII-stage oocyte, adducting to multiple proteins within the cell. The covalent modification of oocyte proteins by these aldehydes increased with extended periods of time postovulation; the mitochondrial protein succinate dehydrogenase (SDHA) was identified as a primary target for 4HNE adduction. Time- and dose-dependent studies revealed that exposure to elevated levels of electrophilic aldehydes causes mitochondrial reactive oxygen species production, lipid peroxidation, loss of mitochondrial membrane potential, and eventual apoptosis within the MII oocyte, presumably as a consequence of electron transport chain collapse following SDHA adduction. Additionally, we have determined that short-term exposure to low doses of 4HNE dramatically impairs the oocyte's ability to participate in fertilization and support embryonic development; however, this loss of functionality can be prevented by supplementation with the antioxidant penicillamine. In conclusion, this study has revealed that the accumulation of electrophilic aldehydes is linked to postovulatory oocyte aging, causing reduced fertility, oxidative stress, and apoptosis of this highly specialized cell. These data highlight the importance of timely fertilization of the mammalian oocyte postovulation and emphasize the potential advantages associated with antioxidant supplementation of oocyte culture medium in circumstances where reinsemination of oocytes may be desirable (i.e., rescue intracytoplasmic sperm injection), or where in vitro fertilization may be delayed. © 2015 by the Society for the Study of Reproduction, Inc.

Prime and boost aerosol exposure via fog machine or shisha smoke followed by cinnamon hypersensitivity and anaphylaxis to spiced food.

PubMed

Jensen-Jarolim, Erika; Roth-Walter, Franziska; Leitner, Erich; Buchleitner, Stefan; Vogelsang, Harald; Kinaciyan, Tamar

2016-01-01

Cinnamon aldehyde (alias cinnamaldehyde) is widely used in food, textile or cosmetic industry. It is mostly associated with contact allergy, but immediate type allergies have been reported. The present study was triggered by a case of anaphylactic events to cinnamon in food and upon skin prick test. We investigated a possible correlation of exposure to a disco fog machine and/or shisha consumption with immediate type hypersensitivity to cinnamon aldehyde in the patient and healthy volunteers. In both fog machines and shisha pipes heating of glycerol-based fluids before evaporation renders chemical transversion to malodorous acrolein. Therefore, both methods are frequently operated with aroma additives. Cinnamon aldehyde and derivatives could be detected by gas chromatography in sampled fog flavored with cola fragrance. The patient as well as healthy (mostly female) volunteers were skin prick tested using cinnamon aldehyde diluted in 0.9 % NaCl, Vaseline® or fog fluid. Persons with a history of exposure to disco fog or shisha (n = 10, mean 32.8 years) reacted with a significantly larger wheal and flare reaction in the skin test (p = 0.0115, p = 0.0146, or p = 0.098) than the non-exposed (n = 8, mean 37.3 years). Both groups were gender matched, but differed in the mean age by 4.5 years. This reaction was specific as compared to skin reactivity to cinnamon alcohol, with only a trend to higher reactivity in exposed persons (ns). From our data we conclude that hapten fragrances such as cinnamon aldehyde may during heating in glycerol fluids associate to complete antigens and via inspiration lead to specific immediate type hypersensitivity. In some cases the hypersensitivity may be unmasked by spiced food containing cinnamon aldehyde or related chemicals, and lead to severe adverse reactions.

Synthesis of C4 and C8 Chemicals from Ethanol on MgO-Incorporated Faujasite Catalysts with Balanced Confinement Effects and Basicity.

PubMed

Zhang, Lu; Pham, Tu N; Faria, Jimmy; Santhanaraj, Daniel; Sooknoi, Tawan; Tan, Qiaohua; Zhao, Zheng; Resasco, Daniel E

2016-04-07

A new type of catalyst has been designed to adjust the basicity and level of molecular confinement of KNaX faujasites by controlled incorporation of Mg through ion exchange and precipitation of extraframework MgO clusters at varying loadings. The catalytic performance of these catalysts was compared in the conversion of C2 and C4 aldehydes to value-added products. The product distribution depends on both the level of acetaldehyde conversion and the fraction of magnesium as extraframework species. These species form rather uniform and highly dispersed nanostructures that resemble nanopetals. Specifically, the sample containing Mg only in the form of exchangeable Mg(2+) ions has much lower activity than those in which a significant fraction of Mg exists as extraframework MgO. Both the (C6+C8)/C4 and C8/C6 ratios increase with additional extraframework Mg at high acetaldehyde conversion levels. These differences in product distribution can be attributed to 1) higher basicity density on the samples with extraframework species, and 2) enhanced confinement inside the zeolite cages in the presence of these species. Additionally, the formation of linear or aromatic C8 aldehyde compounds depends on the position on the crotonaldehyde molecule from which abstraction of a proton occurs. In addition, catalysts with different confinement effects result in different C8 products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of formaldehyde and acrolein in the aqueous samples using a novel needle trap device containing nanoporous silica aerogel sorbent.

PubMed

Barkhordari, Abdullah; Azari, Mansour R; Zendehdel, Rezvan; Heidari, Mahmoud

2017-04-01

In this research, a needle trap device (NTD) packed with nanoporous silica aerogel as a sorbent was used as a new technique for sampling and analysis of formaldehyde and acrolein compounds in aqueous and urine samples. The obtained results were compared with those of the commercial sorbent Carboxen1000. Active sampling was used and a 21-G needle was applied for extraction of gas in the sample headspace. The optimization of experimental parameters like salt addition, temperature and desorption time was done and the performance of the NTD for the extraction of the compounds was evaluated. The optimum temperature and time of desorption were 280 °C and 2 min, respectively. The ranges of limit of detection, limit of quantification and relative standard deviation (RSD) were 0.01-0.03 μg L -1 , 0.03-0.1 μg L -1 and 2.8-7.3%, respectively. It was found that the NTD containing nanoporous silica aerogel had a better performance. Thus, this technique can be applied as an effective and reliable method for sampling and analysis of aldehyde compounds from different biological matrices like urine, exhalation and so on.

Method for the Determination of Carbonyl Compounds in E-Cigarette Aerosols

PubMed Central

Flora, Jason W.; Wilkinson, Celeste T.; Wilkinson, James W.; Lipowicz, Peter J.; Skapars, James A.; Anderson, Adam; Miller, John H.

2017-01-01

Low levels of thermal degradation products such as carbonyls (formaldehyde, acetaldehyde, acrolein, crotonaldehyde) have been reported in e-cigarette aerosols. The collection and analysis of e-cigarette aerosol carbonyls are often adapted from methods developed for tobacco cigarette smoke. These methodologies are often not sensitive enough to detect low carbonyl levels in e-cigarette aerosols. One objective of this work was to develop and validate a rapid, selective and sensitive ultra-performance liquid chromatography with mass spectrometry method optimized for analysis of carbonyls in e-cigarette aerosols. Aerosols were trapped in 20-puff collections, 4-s durations, 55-mL volumes, 30-s intervals, square wave puff profiles. Collection apparatus involved a linear smoking machine with Cambridge filter pad followed by a glass impinger containing acidified 2,4-dinitrophenylhydrazine. This method showed limits of quantitation and detection of 0.016 and 0.003 µg puff−1, respectively, and run time of 4 min. Six e-cigarettes were evaluated (five devices each). All contained measurable levels of carbonyls. Levels were mostly well below those in conventional cigarettes. However, for some e-cigarettes, formaldehyde levels were above those for tobacco cigarettes (highest at 14.1 µg puff−1). Temperatures related to carbonyl yields in e-cigarette aerosols were explored to better understand carbonyl formation: formation of formaldehyde is low at temperatures below 350°C. PMID:28087758

Mechanistic Insights on the Hydrogenation of α,β-Unsaturated Ketones and Aldehydes to Unsaturated Alcohols over Metal Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ide, Matthew S.; Hao, Bing; Neurock, Matthew

The selective hydrogenation of unsaturated ketones (methyl vinyl ketone and benzalacetone) and unsaturated aldehydes (crotonaldehyde and cinnamaldehyde) was carried out with H₂ at 2 bar absolute over Pd/C, Pt/C, Ru/C, Au/C, Au/TiO₂, or Au/Fe₂O₃ catalysts in ethanol or water solvent at 333 K. Comparison of the turnover frequencies revealed Pd/C to be the most active hydrogenation catalyst, but the catalyst failed to produce unsaturated alcohols, indicating hydrogenation of the C=C bond was highly preferred over the C=O bond on Pd. The Pt and Ru catalysts were able to produce unsaturated alcohols from unsaturated aldehydes, but not from unsaturated ketones. Althoughmore » Au/ Fe₂O₃ was able to partially hydrogenate unsaturated ketones to unsaturated alcohols, the overall hydrogenation rate over gold was the lowest of all of the metals examined. First-principles density functional theory calculations were therefore used to explore the reactivity trends of methyl vinyl ketone (MVK) and benzalacetone (BA) hydrogenation over model Pt(111) and Ru(0001) surfaces. The observed selectivity over these metals is likely controlled by the significantly higher activation barriers to hydrogenate the C=O bond compared with those required to hydrogenate the C=C bond. Both the unsaturated alcohol and the saturated ketone, which are the primary reaction products, are strongly bound to Ru and can react further to the saturated alcohol. The lower calculated barriers for the hydrogenation steps over Pt compared with Ru account for the higher observed turnover frequencies for the hydrogenation of MVK and BA over Pt. The presence of a phenyl substituent α to the C=C bond in BA increased the barrier for C=C hydrogenation over those associated with the C=C bond in MVK; however, the increase in barriers with phenyl substitution was not adequate to reverse the selectivity trend.« less

Mitochondria as a source and target of lipid peroxidation products in healthy and diseased heart.

PubMed

Anderson, Ethan J; Katunga, Lalage A; Willis, Monte S

2012-02-01

The heart is a highly oxidative organ in which cardiomyocyte turnover is virtually absent, making it particularly vulnerable to accumulation of lipid peroxidation products (LPP) formed as a result of oxidative damage. Reactive oxygen and nitrogen species are the most common electrophiles formed during lipid peroxidation and lead to the formation of both stable and unstable LPP. Of the LPP formed, highly reactive aldehydes are a well-recognized causative factor in ageing and age-associated diseases, including cardiovascular disease and diabetes. Recent studies have identified that the mitochondria are both a primary source and target of LPP, with specific emphasis on aldehydes in cardiomyocytes and how these affect the electron transport system and Ca(2+) balance. Numerous studies have found that there are functional consequences in the heart following exposure to specific aldehydes (acrolein, trans-2-hexanal, 4-hydroxynonenal and acetaldehyde). Because these LPP are known to form in heart failure, cardiac ischaemia-reperfusion injury and diabetes, they may have an underappreciated role in the pathophysiology of these disease processes. Lipid peroxidation products are involved in the transcriptional regulation of endogenous anti-oxidant systems. Recent evidence demonstrates that transient increases in LPP may be beneficial in cardioprotection by contributing to mitohormesis (i.e. induction of anti-oxidant systems) in cardiomyocytes. Thus, exploitation of the cardioprotective actions of the LPP may represent a novel therapeutic strategy for future treatment of heart disease. © 2011 The Authors. Clinical and Experimental Pharmacology and Physiology © 2011 Blackwell Publishing Asia Pty Ltd.

Molecular Binding Contributes to Concentration Dependent Acrolein Deposition in Rat Upper Airways: CFD and Molecular Dynamics Analyses

PubMed Central

Hu, Qin; Si, Xiuhua April

2018-01-01

Existing in vivo experiments show significantly decreased acrolein uptake in rats with increasing inhaled acrolein concentrations. Considering that high-polarity chemicals are prone to bond with each other, it is hypothesized that molecular binding between acrolein and water will contribute to the experimentally observed deposition decrease by decreasing the effective diffusivity. The objective of this study is to quantify the probability of molecular binding for acrolein, as well as its effects on acrolein deposition, using multiscale simulations. An image-based rat airway geometry was used to predict the transport and deposition of acrolein using the chemical species model. The low Reynolds number turbulence model was used to simulate the airflows. Molecular dynamic (MD) simulations were used to study the molecular binding of acrolein in different media and at different acrolein concentrations. MD results show that significant molecular binding can happen between acrolein and water molecules in human and rat airways. With 72 acrolein embedded in 800 water molecules, about 48% of acrolein compounds contain one hydrogen bond and 10% contain two hydrogen bonds, which agreed favorably with previous MD results. The percentage of hydrogen-bonded acrolein compounds is higher at higher acrolein concentrations or in a medium with higher polarity. Computational dosimetry results show that the size increase caused by the molecular binding reduces the effective diffusivity of acrolein and lowers the chemical deposition onto the airway surfaces. This result is consistent with the experimentally observed deposition decrease at higher concentrations. However, this size increase can only explain part of the concentration-dependent variation of the acrolein uptake and acts as a concurrent mechanism with the uptake-limiting tissue ration rate. Intermolecular interactions and associated variation in diffusivity should be considered in future dosimetry modeling of high-polarity chemicals such as acrolein. PMID:29584651

Acrolein- and 4-Aminobiphenyl-DNA adducts in human bladder mucosa and tumor tissue and their mutagenicity in human urothelial cells

PubMed Central

Weng, Mao-wen; Hu, Yu; Chen, Wei-sheng; Chou, David; Liu, Yan; Donin, Nicholas; Huang, William C.; Lepor, Herbert; Wu, Xue-Ru; Wang, Hailin; Beland, Frederick A.; Tang, Moon-shong

2014-01-01

Tobacco smoke (TS) is a major cause of human bladder cancer (BC). Two components in TS, 4-aminobiphenyl (4-ABP) and acrolein, which also are environmental contaminants, can cause bladder tumor in rat models. Their role in TS related BC has not been forthcoming. To establish the relationship between acrolein and 4-ABP exposure and BC, we analyzed acrolein-deoxyguanosine (dG) and 4-ABP-DNA adducts in normal human urothelial mucosa (NHUM) and bladder tumor tissues (BTT), and measured their mutagenicity in human urothelial cells. We found that the acrolein-dG levels in NHUM and BTT are 10-30 fold higher than 4-ABP-DNA adduct levels and that the acrolein-dG levels in BTT are 2 fold higher than in NHUM. Both acrolein-dG and 4-ABP-DNA adducts are mutagenic; however, the former are 5 fold more mutagenic than the latter. These two types of DNA adducts induce different mutational signatures and spectra. We found that acrolein inhibits nucleotide excision and base excision repair and induces repair protein degradation in urothelial cells. Since acrolein is abundant in TS, inhaled acrolein is excreted into urine and accumulates in the bladder and because acrolein inhibits DNA repair and acrolein-dG DNA adducts are mutagenic, we propose that acrolein is a major bladder carcinogen in TS. PMID:24939871

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sithu, Srinivas D.; Diabetes and Obesity Center, University of Louisville, Louisville, KY 40202; Srivastava, Sanjay

Acrolein is a common air pollutant that is present in high concentrations in wood, cotton, and tobacco smoke, automobile exhaust and industrial waste and emissions. Exposure to acrolein containing environmental pollutants such as tobacco smoke and automobile exhaust has been linked to the activation of the coagulation and hemostasis pathways and thereby to the predisposition of thrombotic events in human. To examine the effects of acrolein on platelets, adult male C57Bl/6 mice were subjected acute (5 ppm for 6 h) or sub-chronic (1 ppm, 6 h/day for 4 days) acrolein inhalation exposures. The acute exposure to acrolein did not causemore » pulmonary inflammation and oxidative stress, dyslipidemia or induce liver damage or muscle injury. Platelet GSH levels in acrolein-exposed mice were comparable to controls, but acrolein-exposure increased the abundance of protein-acrolein adducts in platelets. Platelets isolated from mice, exposed to both acute and sub-chronic acrolein levels, showed increased ADP-induced platelet aggregation. Exposure to acrolein also led to an increase in the indices of platelet activation such as the formation of platelet-leukocyte aggregates in the blood, plasma PF4 levels, and increased platelet-fibrinogen binding. The bleeding time was decreased in acrolein exposed mice. Plasma levels of PF4 were also increased in mice exposed to environmental tobacco smoke. Similar to inhalation exposure, acrolein feeding to mice also increased platelet activation and established a pro-thrombotic state in mice. Together, our data suggest that acrolein is an important contributing factor to the pro-thrombotic risk in human exposure to pollutants such as tobacco smoke or automobile exhaust, or through dietary consumption.« less

Comparison of carcinogen, carbon monoxide, and ultrafine particle emissions from narghile waterpipe and cigarette smoking: Sidestream smoke measurements and assessment of second-hand smoke emission factors

PubMed Central

Daher, Nancy; Saleh, Rawad; Jaroudi, Ezzat; Sheheitli, Hiba; Badr, Thérèse; Sepetdjian, Elizabeth; Al Rashidi, Mariam; Saliba, Najat; Shihadeh, Alan

2009-01-01

The lack of scientific evidence on the constituents, properties, and health effects of second-hand waterpipe smoke has fueled controversy over whether public smoking bans should include the waterpipe. The purpose of this study was to investigate and compare emissions of ultrafine particles (UFP, <100 nm), carcinogenic polyaromatic hydrocarbons (PAH), volatile aldehydes, and carbon monoxide (CO) for cigarettes and narghile (shisha, hookah) waterpipes. These smoke constituents are associated with a variety of cancers, and heart and pulmonary diseases, and span the volatility range found in tobacco smoke. Sidestream cigarette and waterpipe smoke was captured and aged in a 1 m3 Teflon-coated chamber operating at 1.5 air changes per hour (ACH). The chamber was characterized for particle mass and number surface deposition rates. UFP and CO concentrations were measured online using a fast particle spectrometer (TSI 3090 Engine Exhaust Particle Sizer), and an indoor air quality monitor. Particulate PAH and gaseous volatile aldehydes were captured on glass fiber filters and DNPH-coated SPE cartridges, respectively, and analyzed off-line using GC–MS and HPLC–MS. PAH compounds quantified were the 5- and 6-ring compounds of the EPA priority list. Measured aldehydes consisted of formaldehyde, acetaldehyde, acrolein, methacrolein, and propionaldehyde. We found that a single waterpipe use session emits in the sidestream smoke approximately four times the carcinogenic PAH, four times the volatile aldehydes, and 30 times the CO of a single cigarette. Accounting for exhaled mainstream smoke, and given a habitual smoker smoking rate of 2 cigarettes per hour, during a typical one-hour waterpipe use session a waterpipe smoker likely generates ambient carcinogens and toxicants equivalent to 2–10 cigarette smokers, depending on the compound in question. There is therefore good reason to include waterpipe tobacco smoking in public smoking bans. PMID:20161525

Comparison of carcinogen, carbon monoxide, and ultrafine particle emissions from narghile waterpipe and cigarette smoking: Sidestream smoke measurements and assessment of second-hand smoke emission factors

NASA Astrophysics Data System (ADS)

Daher, Nancy; Saleh, Rawad; Jaroudi, Ezzat; Sheheitli, Hiba; Badr, Thérèse; Sepetdjian, Elizabeth; Al Rashidi, Mariam; Saliba, Najat; Shihadeh, Alan

2010-01-01

The lack of scientific evidence on the constituents, properties, and health effects of second-hand waterpipe smoke has fueled controversy over whether public smoking bans should include the waterpipe. The purpose of this study was to investigate and compare emissions of ultrafine particles (UFP, <100 nm), carcinogenic polyaromatic hydrocarbons (PAH), volatile aldehydes, and carbon monoxide (CO) for cigarettes and narghile (shisha, hookah) waterpipes. These smoke constituents are associated with a variety of cancers, and heart and pulmonary diseases, and span the volatility range found in tobacco smoke. Sidestream cigarette and waterpipe smoke was captured and aged in a 1 m 3 Teflon-coated chamber operating at 1.5 air changes per hour (ACH). The chamber was characterized for particle mass and number surface deposition rates. UFP and CO concentrations were measured online using a fast particle spectrometer (TSI 3090 Engine Exhaust Particle Sizer), and an indoor air quality monitor. Particulate PAH and gaseous volatile aldehydes were captured on glass fiber filters and DNPH-coated SPE cartridges, respectively, and analyzed off-line using GC-MS and HPLC-MS. PAH compounds quantified were the 5- and 6-ring compounds of the EPA priority list. Measured aldehydes consisted of formaldehyde, acetaldehyde, acrolein, methacrolein, and propionaldehyde. We found that a single waterpipe use session emits in the sidestream smoke approximately four times the carcinogenic PAH, four times the volatile aldehydes, and 30 times the CO of a single cigarette. Accounting for exhaled mainstream smoke, and given a habitual smoker smoking rate of 2 cigarettes per hour, during a typical one-hour waterpipe use session a waterpipe smoker likely generates ambient carcinogens and toxicants equivalent to 2-10 cigarette smokers, depending on the compound in question. There is therefore good reason to include waterpipe tobacco smoking in public smoking bans.

Aldehyde-alcohol reactions catalyzed under mild conditions by chromium(III) terephthalate metal organic framework (MIL-101) and phosphotungstic acid composites.

PubMed

Bromberg, Lev; Hatton, T Alan

2011-12-01

Porous materials based on chromium(III) terephthalate metal organic frameworks (MIL-101) and their composites with phosphotungstic acid (PTA) were studied as heterogeneous acid catalysts in aldehyde-alcohol reactions exemplified by acetaldehyde-phenol (A-P) condensation and dimethylacetal formation from benzaldehyde and methanol (B-M reaction). The MIL-101 was synthesized solvothermically in water, and the MIL101/PTA composite materials were obtained by either impregnation of the already prepared MIL-101 porous matrix with phosphotungstic acid solution or by solvothermic treatment of aqueous mixtures of Cr(NO(3))(3), and terephthalic and phosphotungstic acids. The MIL101/PTA materials appeared to be effective catalysts for both A-P and B-M reactions occurring at room temperature, with half-lives ranging from 0.5 h (A-P) to 1.5-2 h (B-M) and turnover numbers over 600 for A-P and over 2900 for the B-M reaction, respectively. A synergistic effect of the strong acidic moieties (PTA) addition to mildly acidic Brønsted and Lewis acid cites of the MIL-101 was observed with the MIL101/PTA composites. The ability of the PTA and MIL101/PTA materials to strongly absorb and condense acetaldehyde vapors was discovered, with the MIL101/PTA absorbing over 10-fold its dry weight of acetaldehyde condensate at room temperature. The acetaldehyde was converted rapidly to crotonaldehyde and higher-molecular-weight compounds while in contact with MIL-101 and MIL101/PTA materials. The stability of the MIL-101 and MIL101/PTA catalysts was assessed within four cycles of the 1-day alcohol-aldehyde reactions in terms of the overall catalyst recovery, PTA or Cr content, and reaction rate constants in each cycle. The loss of the catalyst over 4 cycles was approximately 10 wt % for all tested catalysts due to the incomplete recovery and minute dissolution of the components. The reaction rates in all cycles remained unchanged and the catalyst losses stopped after the third cycle. The developed MIL101/PTA composites appear to be feasible for industrial catalytic applications. © 2011 American Chemical Society

The selective hydrogenation of crotonaldehyde over bimetallic catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schoeb, Ann M.

1997-10-17

The selective hydrogenation of crotonaldehyde has been investigated over a monometallic Pt/SiO 2 catalyst and platinum bimetallic catalysts where the second metal was either silver, copper, or tin. The effects of addition of a second metal to the Pt/SiO 2 system on the selectivity to crotyl alcohol were investigated. The Pt-Sn bimetallic catalysts were characterized by hydrogen chemisorption, 1H NMR and microcalorimetry. The Pt-Ag/SiO 2 and Pt-Cu/SiO 2 catalysts were characterized by hydrogen chemisorption. Pt-Sn/SiO 2 catalysts selectively hydrogenated crotonaldehyde to crotyl alcohol and the method of preparation of these catalysts affected the selectivity. The most selective Pt-Sn/SiO 2 catalystsmore » for the hydrogenation of crotonaldehyde to crotyl alcohol were those in which the Sn precursor was dissolved in a HCl solution. Sn increased both the rate of formation of butyraldehyde and the rate of formation of crotyl alcohol. The Pt/SiO 2, Pt-Ag/SiO 2 and Pt-Cu/SiO 2 catalysts produced only butyraldehyde. Initial heats of adsorption (~90 kJ/mol) measured using microcalorimetry were not affected by the presence of Sn on Pt. We can conclude that there is no through metal electronic interaction between Pt and Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn at least with respect to hydrogen surface bonds since the Pt and Pt-Sn had similar initial heats of adsorption coupled with the invariance of the 1H NMR Knight shift.« less

Protective effect of ALDH2 against cyclophosphamide-induced acute hepatotoxicity via attenuating oxidative stress and reactive aldehydes.

PubMed

Zhai, Xiaoxuan; Zhang, Zhenxiao; Liu, Wenwen; Liu, Baoshan; Zhang, Rui; Wang, Wenjun; Zheng, Wen; Xu, Feng; Wang, Jiali; Chen, Yuguo

2018-04-30

Cyclophosphamide (CY) is a widely used chemotherapeutic agent that is associated with severe side effects, such as hepatotoxicity and nephrotoxicity. However, the extent, mechanisms and potential prevention and treatment strategies of CY-induced acute hepatotoxicity and nephrotoxicity are largely unknown. In this study, we determined the existence and extent of CY-induced acute hepatotoxicity and nephrotoxicity, and demonstrated the effect of ALDH2 on CY-induced acute tissue toxicity and related mechanisms. Adult male C57BL/6J (wide-type, WT) and ALDH2 -/- (KO) mice were divided into four groups: WT, WT + CY, KO + CY and WT + CY + Alda-1. Biochemical analysis showed that plasma ALT was increased by 35.8% in KO + CY group and decreased by 21.1% in WT + CY + Alda-1 group compared to WT + CY group (P < 0.05, respectively). However, there was no significant difference among WT, WT + CY and KO + CY groups regarding plasma renal marker enzymes, including blood urea nitrogen (BUN), creatinine and cystatin C (CysC). Levels of reactive oxygen species (ROS) and toxic aldehydes (acrolein, 4-hydroxynonenol and malondialdehyde) were increased significantly in KO + CY group and decreased significantly in WT + CY + Alda-1 group compared to WT + CY group (P < 0.05, respectively). These findings demonstrate that CY could induce acute hepatotoxicity without nephrotoxicity, and ALDH2 plays a protective role in CY-induced acute hepatotoxicity. The underlying mechanisms are associated with attenuating oxidative stress and detoxifying reactive aldehydes. Copyright © 2018 Elsevier Inc. All rights reserved.

Potentiation of pulmonary reflex response to capsaicin 24h following whole-body acrolein exposure is mediated by TRPV1.

PubMed

Hazari, Mehdi S; Rowan, William H; Winsett, Darrell W; Ledbetter, Allen D; Haykal-Coates, Najwa; Watkinson, William P; Costa, Daniel L

2008-02-01

Pulmonary C-fibers are stimulated by irritant air pollutants producing apnea, bronchospasm, and decrease in HR. Chemoreflex responses resulting from C-fiber activation are sometimes mediated by TRPV1 and release of substance P. While acrolein has been shown to stimulate C-fibers, the persistence of acrolein effects and the role of C-fibers in these responses are unknown. These experiments were designed to determine the effects of whole-body acrolein exposure and pulmonary chemoreflex response post-acrolein. Rats were exposed to either air or 3 ppm acrolein for 3 h while ventilatory function and HR were measured; 1-day later response to capsaicin challenge was measured in anesthetized rats. Rats experienced apnea and decrease in HR upon exposure to acrolein, which was not affected by either TRPV1 antagonist or NK(1)R antagonist pretreatment. Twenty-four hours later, capsaicin caused apnea and bronchoconstriction in control rats, which was potentiated in rats exposed to acrolein. Pretreatment with TRPV1 antagonist or NK(1)R antagonist prevented potentiation of apneic response and bronchoconstriction 24h post-exposure. These data suggest that although potentiation of pulmonary chemoreflex response 24h post-acrolein is mediated by TRPV1 and release of substance P, cardiopulmonary inhibition during whole-body acrolein exposure is mediated through other mechanisms.

Comparison of the impact of the Tobacco Heating System 2.2 and a cigarette on indoor air quality.

PubMed

Mitova, Maya I; Campelos, Pedro B; Goujon-Ginglinger, Catherine G; Maeder, Serge; Mottier, Nicolas; Rouget, Emmanuel G R; Tharin, Manuel; Tricker, Anthony R

2016-10-01

The impact of the Tobacco Heating System 2.2 (THS 2.2) on indoor air quality was evaluated in an environmentally controlled room using ventilation conditions recommended for simulating "Office", "Residential" and "Hospitality" environments and was compared with smoking a lit-end cigarette (Marlboro Gold) under identical experimental conditions. The concentrations of eighteen indoor air constituents (respirable suspended particles (RSP) < 2.5 μm in diameter), ultraviolet particulate matter (UVPM), fluorescent particulate matter (FPM), solanesol, 3-ethenylpyridine, nicotine, 1,3-butadiene, acrylonitrile, benzene, isoprene, toluene, acetaldehyde, acrolein, crotonaldehyde, formaldehyde, carbon monoxide, nitrogen oxide, and combined oxides of nitrogen) were measured. In simulations evaluating THS 2.2, the concentrations of most studied analytes did not exceed the background concentrations determined when non-smoking panelists were present in the environmentally controlled room under equivalent conditions. Only acetaldehyde and nicotine concentrations were increased above background concentrations in the "Office" (3.65 and 1.10 μg/m(3)), "Residential" (5.09 and 1.81 μg/m(3)) and "Hospitality" (1.40 and 0.66 μg/m(3)) simulations, respectively. Smoking Marlboro Gold resulted in greater increases in the concentrations of acetaldehyde (58.8, 83.8 and 33.1 μg/m(3)) and nicotine (34.7, 29.1 and 34.6 μg/m(3)) as well as all other measured indoor air constituents in the "Office", "Residential" and "Hospitality" simulations, respectively. Copyright © 2016 The Author(s). Published by Elsevier Inc. All rights reserved.

Protocol to assess the impact of tobacco-induced volatile organic compounds on cardiovascular risk in a cross- sectional cohort: Cardiovascular Injury due to Tobacco Use study

PubMed Central

Keith, Rachel J; Fetterman, Jessica L; Riggs, Daniel W; O’Toole, Timothy; Nystoriak, Jessica L; Holbrook, Monika; Lorkiewicz, Pawel; Bhatnagar, Aruni; DeFilippis, Andrew P; Hamburg, Naomi M

2018-01-01

Introduction Tobacco use leads to increased mortality, the majority of which is attributed to cardiovascular disease. Despite this knowledge, the early cardiovascular impact of tobacco product use is not well understood. Tobacco use increases exposure to harmful and potentially harmful constituents including volatile organic compounds (VOCs) such as acrolein and crotonaldehyde, which may contribute to cardiovascular risk. The link between exposure patterns, risk profiles and demographic distribution of tobacco product users, particularly users of new and emerging products, are not well known. Therefore, we designed the Cardiovascular Injury due to Tobacco Use (CITU) study to assess population characteristics, demographic features, exposure patterns and cardiovascular risk in relation to tobacco. Methods and analysis We present the design and methodology of the CITU study, a cross-sectional observational tobacco study conducted in Boston, Massachusetts and Louisville, Kentucky starting in 2014. Healthy participants 21–45 years of age who use tobacco products, including electronic nicotine devices, or who never used tobacco are being recruited. The study aims to recruit an evenly split cohort of African-Americans and Caucasians, that is, sex balanced for evaluation of self-reported tobacco exposure, VOC exposure and tobacco-induced injury profiling. Detailed information about participant’s demographics, health status and lifestyle is also collected. Ethics and dissemination The study protocol was approved institutional review boards at both participating universities. All study protocols will protect participant confidentiality. Results from the study will be disseminated via peer-reviewed journals and presented at scientific conferences. PMID:29602846

Inhalation Toxicology. X., Times to incapacitation for rats exposed continuously to carbon monoxide, acrolein, and to carbon monoxide-acrolein mixtures.

DOT National Transportation Integrated Search

1990-12-01

Laboratory rats were exposed to experimental atmospheres of (a) carbon monoxide (CO) in air, (b) acrolein in air, and (c) to mixtures of CO and acrolein in air. The toxic potency of each of the three types of environments was evaluated toxicokinetica...

Acrolein increases airway sensitivity to substance P and decreases NEP activity in guinea pigs.

PubMed

Turner, C R; Stow, R B; Hubbs, S J; Gomes, B C; Williams, J C

1993-04-01

The effects of acrolein exposure on airway responses to intravenous substance P were determined in guinea pigs exposed to vehicle or 1.6 ppm acrolein for 7.5 h on 2 consecutive days and examined 1, 4, 8, 15, and 28 days after exposure by use of pulmonary mechanics and bronchoalveolar lavage (BAL). Lung, trachea, liver, and BAL fluid were also assayed for neutral endopeptidase (NEP) activity 1, 7, and 28 days after exposure. Pulmonary inflammation and epithelial damage were prominent 1 day after acrolein exposure. NEP activity was decreased in the lungs, trachea, and liver 1 and 7 days after acrolein. Twenty-eight days after exposure, NEP activity in the lungs and liver was not significantly different in vehicle- and acrolein-exposed guinea pigs but was still reduced in tracheal tissue. The BAL NEP activity in acrolein-exposed guinea pigs was approximately twice that of vehicle control guinea pigs at all three time points. Acrolein caused a prolonged increase in airway sensitivity to substance P. Experiments performed in the presence of thiorphan suggested that the acrolein-induced reduction in NEP may contribute to increased airway sensitivity to aerosolized substance P, but the increase in airway sensitivity to intravenous substance P may occur by additional mechanisms.

Acrolein increases 5-lipoxygenase expression in murine macrophages through activation of ERK pathway

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Chae E.; Lee, Seung J.; Seo, Kyo W.

2010-05-15

Episodic exposure to acrolein-rich pollutants has been linked to acute myocardial infarction, and 5-lipoxygenase (5-LO) is involved in the production of matrix metalloproteinase-9 (MMP-9), which destabilizes atherosclerotic plaques. Thus, the present study determined the effect of acrolein on 5-LO/leukotriene B{sub 4} (LTB{sub 4}) production in murine macrophages. Stimulation of J774A.1 cells with acrolein led to increased LTB{sub 4} production in association with increased 5-LO expression. Acrolein-evoked 5-LO expression was blocked by pharmacological inhibition of the ERK pathway, but not by inhibitors for JNK and p38 MAPK pathways. In line with these results, acrolein exclusively increased the phosphorylation of ERK amongmore » these MAPK, suggesting a role for the ERK pathway in acrolein-induced 5-LO expression with subsequent production of LTB{sub 4}. Among the receptor tyrosine kinases including epidermal growth factor receptor (EGFR) and platelet derived growth factor receptor (PDGFR), acrolein-evoked ERK phosphorylation was attenuated by AG1478, an EGFR inhibitor, but not by AG1295, a PDGFR inhibitor. In addition, acrolein-evoked 5-LO expression was also inhibited by inhibition of EGFR pathway, but not by inhibition of PDGFR pathway. These observations suggest that acrolein has a profound effect on the 5-LO pathway via an EGFR-mediated activation of ERK pathway, leading to acute ischemic syndromes through the generation of LTB{sub 4}, subsequent MMP-9 production and plaque rupture.« less

Proposed Mode of Action for Acrolein Respiratory Toxicity Associated with Inhaled Tobacco Smoke.

PubMed

Yeager, R Philip; Kushman, Mary; Chemerynski, Susan; Weil, Roxana; Fu, Xin; White, Marcella; Callahan-Lyon, Priscilla; Rosenfeldt, Hans

2016-06-01

This article presents a mode of action (MOA) analysis that identifies key mechanisms in the respiratory toxicity of inhaled acrolein and proposes key acrolein-related toxic events resulting from the inhalation of tobacco smoke. Smoking causes chronic obstructive pulmonary disorder (COPD) and acrolein has been previously linked to the majority of smoking-induced noncancer respiratory toxicity. In contrast to previous MOA analyses for acrolein, this MOA focuses on the toxicity of acrolein in the lower respiratory system, reflecting the exposure that smokers experience upon tobacco smoke inhalation. The key mechanisms of acrolein toxicity identified in this proposed MOA include (1) acrolein chemical reactivity with proteins and other macromolecules of cells lining the respiratory tract, (2) cellular oxidative stress, including compromise of the important anti-oxidant glutathione, (3) chronic inflammation, (4) necrotic cell death leading to a feedback loop where necrosis-induced inflammation leads to more necrosis and oxidative damage and vice versa, (5) tissue remodeling and destruction, and (6) loss of lung elasticity and enlarged lung airspaces. From these mechanisms, the proposed MOA analysis identifies the key cellular processes in acrolein respiratory toxicity that consistently occur with the development of COPD: inflammation and necrosis in the middle and lower regions of the respiratory tract. Moreover, the acrolein exposures that occur as a result of smoking are well above exposures that induce both inflammation and necrosis in laboratory animals, highlighting the importance of the role of acrolein in smoking-related respiratory disease. Published by Oxford University Press on behalf of the Society of Toxicology 2016. This work is written by US Government employees and is in the public domain in the US.

Activation of MMP-9 activity by acrolein in saliva from patients with primary Sjögren's syndrome and its mechanism.

PubMed

Uemura, Takeshi; Suzuki, Takehiro; Saiki, Ryotaro; Dohmae, Naoshi; Ito, Satoshi; Takahashi, Hoyu; Toida, Toshihiko; Kashiwagi, Keiko; Igarashi, Kazuei

2017-07-01

We have recently reported that the altered recognition patterns of immunoglobulins due to acrolein conjugation are at least partially responsible for autoimmune diseases in patients with primary Sjögren's syndrome (pSS). In the current study, it was found that the specific activity (activity/ng protein) of metalloproteinase-9 (MMP-9) in saliva was elevated about 2.4-fold in pSS patients. Accordingly, it was examined whether MMP-9 is activated by acrolein. It was found that the MMP-9 with 92kDa molecular weight was activated by acrolein. Under the conditions studied, Cys99, located in the propeptide, was conjugated with acrolein together with Cys230, 244, 302, 314, 329, 347, 361, 373, 388 and 516, which are located in fibronectin repeats and glycosyl domains, but not on the active site of MMP-9. In addition, 82 and 68kDa constructs of MMP-9s, lacking the NH 2 -terminal domain that contains Cys99, were not activated by acrolein. The results suggest that acrolein conjugation at Cys99 caused the active site of MMP-9 to be exposed. Activation of MMP-9 by acrolein was inhibited by cysteine, and slightly by lysine, because these amino acids inhibited acrolein conjugation with MMP-9. Conversely, MMP-9 activity in the presence of 50μM acrolein was enhanced by 100μM histidine. This was due to the inhibition of acrolein conjugation with His405 and 411 located at the Zn 2+ binding site of MMP-9. These results suggest that activation of 92kDa MMP-9 by acrolein is involved in tissue damage in pSS patients and is regulated by cysteine and histidine, and slightly by lysine. Activated 82 and 68kDa MMP-9s were not detected in saliva of pSS patients by Western blotting. Copyright © 2017 Elsevier Ltd. All rights reserved.

Oxidative and reductive metabolism of lipid-peroxidation derived carbonyls

PubMed Central

Singh, Mahavir; Kapoor, Aniruddh; Bhatnagar, Aruni

2015-01-01

Extensive research has shown that increased production of reactive oxygen species (ROS) results in tissue injury under a variety of pathological conditions and chronic degenerative diseases. While ROS are highly reactive and can incite significant injury, polyunsaturated lipids in membranes and lipoproteins are their main targets. ROS-triggered lipid peroxidation reactions generate a range of reactive carbonyl species (RCS), and these RCS spread and amplify ROS-related injury. Several RCS generated in oxidizing lipids, such as 4-hydroxy trans-2-nonenal (HNE), 4-oxo-2-(E)-nonenal (ONE), acrolein, malondialdehyde (MDA) and phospholipid aldehydes have been shown to be produced under conditions of oxidative stress and contribute to tissue injury and dysfunction by depleting glutathione and other reductants leading to the modification of proteins, lipids, and DNA. To prevent tissue injury, these RCS are metabolized by several oxidoreductases, including members of the aldo-keto reductase (AKR) superfamily, aldehyde dehydrogenases (ALDHs), and alcohol dehydrogenases (ADHs). Metabolism via these enzymes results in RCS inactivation and detoxification, although under some conditions, it can also lead to the generation of signaling molecules that trigger adaptive responses. Metabolic transformation and detoxification of RCS by oxidoreductases prevent indiscriminate ROS toxicity, while at the same time, preserving ROS signaling. A better understanding of RCS metabolism by oxidoreductases could lead to the development of novel therapeutic interventions to decrease oxidative injury in several disease states and to enhance resistance to ROS-induced toxicity. PMID:25559856

Acrolein contributes strongly to antimicrobial and heterocyclic amine transformation activities of reuterin.

PubMed

Engels, Christina; Schwab, Clarissa; Zhang, Jianbo; Stevens, Marc J A; Bieri, Corinne; Ebert, Marc-Olivier; McNeill, Kristopher; Sturla, Shana J; Lacroix, Christophe

2016-11-07

Glycerol/diol dehydratases catalyze the conversion of glycerol to 3-hydroxypropionaldehyde (3-HPA), the basis of a multi-component system called reuterin. Reuterin has antimicrobial properties and undergoes chemical conjugation with dietary heterocyclic amines (HCAs). In aqueous solution reuterin is in dynamic equilibrium with the toxicant acrolein. It was the aim of this study to investigate the extent of acrolein formation at various physiological conditions and to determine its role in biological and chemical activities. The application of a combined novel analytical approach including IC-PAD, LC-MS and NMR together with specific acrolein scavengers suggested for the first time that acrolein, and not 3-HPA, is the active compound responsible for HCA conjugation and antimicrobial activity attributed to reuterin. As formation of the HCA conjugate was observed in vivo, our results imply that acrolein is formed in the human gut with implications on detoxification of HCAs. We propose to re-define the term reuterin to include acrolein.

Effects of acrolein on aldosterone release from zona glomerulosa cells in male rats.

PubMed

Wang, Kai-Lee; Huang, Wen-Ching; Chou, Jou-Chun; Weng, Ting-Chun; Hu, Sindy; Lieu, Fu-Kong; Lai, Wei-Ho; Idova, Galina; Wang, Paulus S; Wang, Shyi-Wu

2016-07-01

A positive correlation between smoking and hypertension has been well established. Acrolein is a major toxic volatile compound found in cigarette smoke. Human exposure to low levels of acrolein is unavoidable due to its production in daily activities, such as smoke from industrial, hot oil cooking vapors, and exhaust fumes from vehicles. The toxicity and the action mechanism of acrolein to induce apoptosis have been extensively studied, but the effects of acrolein on hypertension are still unknown. The present study aimed to examine the effects of acrolein on aldosterone release both in vivo and in vitro. Male rats were divided into three groups, and intraperitoneally injected with normal saline, or acrolein (2mg/kg) for 1 (group A-1) or 3 (group A-3) days, respectively. After sacrificing, rat blood samples were obtained to measure plasma aldosterone and angiotensin II (Ang II) levels. Zona glomerulosa (ZG) cells were prepared from rat adrenal cortex, and were incubated with or without stimulants. We found that the serum aldosterone was increased by 1.2-fold (p<0.05) in A-3 group as compared to control group. Basal aldosterone release from ZG cells in A-3 group was also increased significantly. Moreover, acrolein enhanced the stimulatory effects of Ang II and 8-bromo-cyclic AMP on aldosterone secretion from ZG cells prepared in both A-1 and A-3 groups. Furthermore, the enzyme activity of P450scc, the rate-limiting step of aldosterone synthesis, was elevated after acrolein injection. Plasma level of Ang II was increased in both A-1 and A-3 groups. These results suggested that acrolein exposure increased aldosterone production, at least in part, through elevating the level of plasma Ang II and stimulating steroidogenesis pathways. Copyright © 2016 Elsevier Inc. All rights reserved.

Determination of acrolein in french fries by solid-phase microextraction gas chromatography and mass spectrometry.

PubMed

Osório, Vanessa Moreira; de Lourdes Cardeal, Zenilda

2011-05-27

The frying of foods in the home can be a cause of indoor pollution due to the formation of acrolein. The emission of acrolein formed during frying in soybean, corn, canola, sunflower and palm oils was studied. A GC/MS method has been developed to determine acrolein in French fries using SPME as the sampling technique after derivatization with 2,4-dinitrophenylhydrazine (DNPH). Optimum SPME conditions included desorption at 250°C for 2min after an adsorption time of 10min at room temperature. The method presented good resolution, repeatability, detection and quantification limits, and linearity of response. French fries were prepared in five different oils with four frying steps. The results showed that changes in acrolein concentration occurred after frying potatoes in different types of oil and at different frying cycles. Potatoes fried in soybean oil contained the lowest concentration of acrolein. Shoestring potatoes contained a lower concentration of acrolein than potato chips and French fries, respectively, because of the higher surface/volume ratio. Copyright © 2010 Elsevier B.V. All rights reserved.

Development of two stable isotope dilution assays for the quantitation of acrolein in heat-processed fats.

PubMed

Ewert, Alice; Granvogl, Michael; Schieberle, Peter

2011-04-27

Two stable isotope dilution assays were developed for the quantitation of acrolein in fats and oils using [(13)C(3)]-acrolein as the internal standard. First, a direct GC-MS headspace method, followed by an indirect GC-MS method using derivatization with pentafluorophenyl hydrazine, was established. Analysis of six different types of oils varying in their pattern of fatty acids showed significant differences in the amounts of acrolein formed after heating at various temperatures and for various times. For example, after 24 h at 140 °C, coconut oil contained 6.7 mg/kg, whereas linseed oil was highest with 242.3 mg/kg. A comparison of the results showed that the extent of acrolein formation seemed to be correlated with the amount of linolenic acid in the oils. Although the acrolein concentrations were lowered in all six oils after frying of potato crisps, linseed and rapeseed oil still contained the highest amounts of acrolein after frying. By applying both methods on different thermally treated fats and oils, nearly identical quantitative data were obtained.

In vitro attenuation of acrolein-induced toxicity by phloretin, a phenolic compound from apple.

PubMed

Zhu, Qin; Zhang, Natalie Qi-Shan; Lau, Chi Fai; Chao, Jianfei; Sun, Zheng; Chang, Raymond Chuen-Chung; Chen, Feng; Wang, Mingfu

2012-12-01

In the current study, the protective effects of phloretin were investigated in acrolein-challenged amino acid, protein, and cell models. It was found that the formation of FDP-lysine (a typical acrolein-lysine adduct) was strongly inhibited in the presence of phloretin and the remaining electrophilic site in FDP-lysine was also blocked by phloretin. Moreover, direct trapping of acrolein by phloretin was found to be responsible for inhibiting the incorporation of carbonyl groups into BSA and oligomerisation in RNase A. Subsequently, the reduction of LDH release in human neuroblastoma SH-SY5Y cells under acrolein challenge suggested the cytoprotective effects of phloretin. Such protection might be mediated through inhibiting the increased cellular protein carbonyl level as revealed by Western blotting analysis. The present study highlighted an apple phenolic compound, phloretin as a promising candidate in prevention or treatment of acrolein-associated human diseases. Copyright © 2012 Elsevier Ltd. All rights reserved.

IRIS Toxicological Review of Acrolein (2003 Final)

EPA Science Inventory

EPA announced the release of the final report, Toxicological Review of Acrolein: in support of the Integrated Risk Information System (IRIS). The updated Summary for Acrolein and accompanying toxicological review have been added to the IRIS Database.

Protocol to assess the impact of tobacco-induced volatile organic compounds on cardiovascular risk in a cross- sectional cohort: Cardiovascular Injury due to Tobacco Use study.

PubMed

Keith, Rachel J; Fetterman, Jessica L; Riggs, Daniel W; O'Toole, Timothy; Nystoriak, Jessica L; Holbrook, Monika; Lorkiewicz, Pawel; Bhatnagar, Aruni; DeFilippis, Andrew P; Hamburg, Naomi M

2018-03-30

Tobacco use leads to increased mortality, the majority of which is attributed to cardiovascular disease. Despite this knowledge, the early cardiovascular impact of tobacco product use is not well understood. Tobacco use increases exposure to harmful and potentially harmful constituents including volatile organic compounds (VOCs) such as acrolein and crotonaldehyde, which may contribute to cardiovascular risk. The link between exposure patterns, risk profiles and demographic distribution of tobacco product users, particularly users of new and emerging products, are not well known. Therefore, we designed the Cardiovascular Injury due to Tobacco Use (CITU) study to assess population characteristics, demographic features, exposure patterns and cardiovascular risk in relation to tobacco. We present the design and methodology of the CITU study, a cross-sectional observational tobacco study conducted in Boston, Massachusetts and Louisville, Kentucky starting in 2014. Healthy participants 21-45 years of age who use tobacco products, including electronic nicotine devices, or who never used tobacco are being recruited. The study aims to recruit an evenly split cohort of African-Americans and Caucasians, that is, sex balanced for evaluation of self-reported tobacco exposure, VOC exposure and tobacco-induced injury profiling. Detailed information about participant's demographics, health status and lifestyle is also collected. The study protocol was approved institutional review boards at both participating universities. All study protocols will protect participant confidentiality. Results from the study will be disseminated via peer-reviewed journals and presented at scientific conferences. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Quantitative Infrared Absorption Spectra and Vibrational Assignments of Crotonaldehyde and Methyl Vinyl Ketone Using Gas-Phase Mid-Infrared, Far-Infrared, and Liquid Raman Spectra: s-cis vs s-trans Composition Confirmed via Temperature Studies and ab Initio Methods.

PubMed

Lindenmaier, Rodica; Williams, Stephen D; Sams, Robert L; Johnson, Timothy J

2017-02-16

Methyl vinyl ketone (MVK) and crotonaldehyde are chemical isomers; both are also important species in tropospheric chemistry. We report quantitative vapor-phase infrared spectra of crotonaldehyde and MVK vapors over the 540-6500 cm -1 range. Vibrational assignments of all fundamental modes are made for both molecules on the basis of far- and mid-infrared vapor-phase spectra, liquid Raman spectra, along with density functional theory and ab initio MP2 and high energy-accuracy compound theoretical models (W1BD). Theoretical results indicate that at room temperature the crotonaldehyde equilibrium mixture is approximately 97% s-trans and only 3% s-cis conformer. Nearly all observed bands are thus associated with the s-trans conformer, but a few appear to be uniquely associated with the s-cis conformer, notably ν 16 c at 730.90 cm -1 , which displays a substantial intensity increase with temperature (70% upon going from 5 to 50 o C). The intensity of the corresponding mode of the s-trans conformer decreases with temperature. Under the same conditions, the MVK equilibrium mixture is approximately 69% s-trans conformer and 31% s-cis. W1BD calculations indicate that for MVK this is one of those (rare) cases where there are comparable populations of both conformers, approximately doubling the number of observed bands and exacerbating the vibrational assignments. We uniquely assign the bands associated with both the MVK s-cis conformer as well as those of the s-trans, thus completing the vibrational analyses of both conformers from the same set of experimental spectra. Integrated band intensities are reported for both molecules along with global warming potential values. Using the quantitative IR data, potential bands for atmospheric monitoring are also discussed.

Quantitative Infrared Absorption Spectra and Vibrational Assignments of Crotonaldehyde and Methyl Vinyl Ketone Using Gas-Phase Mid-Infrared, Far-Infrared, and Liquid Raman Spectra: s-cis vs s-trans Composition Confirmed via Temperature Studies and ab Initio Methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindenmaier, Rodica; Williams, Stephen D.; Sams, Robert L.

Methyl vinyl ketone (MVK) and crotonaldehyde are chemical isomers; both are also important species in tropospheric chemistry. We report quantitative vapor-phase infrared spectra of crotonaldehyde and MVK vapors over the 540-6500 cm-1 range. Vibrational assignments of all fundamental modes are made for both molecules based on far- and mid-infrared vapor-phase spectra, liquid Raman spectra, along with density functional theory and ab initio MP2 and high energy-accuracy compound theoretical models (W1BD). Theoretical results indicate that at room temperature the crotonaldehyde equilibrium mixture is approximately 97% s-trans and only 3% s-cis conformer. Nearly all observed bands are thus associated with the s-transmore » conformer, but a few appear to be uniquely associated the s-cis conformer, notably ν16c at 730.90 cm-1, which displays a substantial intensity increase with temperature (62% upon going from 5 to 50 oC). The intensity of the corresponding mode of the s-trans conformer decreases with temperature. Under the same conditions, the MVK equilibrium mixture is approximately 69% s-trans conformer and 31% s-cis. W1BD calculations indicate that for MVK this is one of those (rare) cases where there are comparable populations of both conformers, ~doubling the number of observed bands and exacerbating the vibrational assignments. We uniquely assign the bands associated with both the MVK s-cis conformer as well as those of the s-trans, thus completing the vibrational analyses of both conformers from the same set of experimental spectra. Integrated band intensities are reported for both molecules along with global warming potential values. Using the quantitative IR data, potential bands for atmospheric monitoring are also discussed.« less

Glutathione-S-transferase P protects against endothelial dysfunction induced by exposure to tobacco smoke.

PubMed

Conklin, Daniel J; Haberzettl, Petra; Prough, Russell A; Bhatnagar, Aruni

2009-05-01

Exposure to tobacco smoke impairs endothelium-dependent arterial dilation. Reactive constituents of cigarette smoke are metabolized and detoxified by glutathione-S-transferases (GSTs). Although polymorphisms in GST genes are associated with the risk of cancer in smokers, the role of these enzymes in regulating the cardiovascular effects of smoking has not been studied. The P isoform of GST (GSTP), which catalyzes the conjugation of electrophilic molecules in cigarette smoke such as acrolein, was expressed in high abundance in the mouse lung and aorta. Exposure to tobacco smoke for 3 days (5 h/day) decreased total plasma protein. These changes were exaggerated in GSTP(-/-) mice. Aortic rings isolated from tobacco smoke-exposed GSTP(-/-) mice showed greater attenuation of ACh-evoked relaxation than those from GSTP(+/+) mice. The lung, plasma, and aorta of mice exposed to tobacco smoke or acrolein (for 5 h) accumulated more acrolein-adducted proteins than those tissues of mice exposed to air, indicating that exposure to tobacco smoke results in the systemic delivery of acrolein. Relative to GSTP(+/+) mice, modification of some proteins by acrolein was increased in the aorta of GSTP(-/-) mice. Aortic rings prepared from GSTP(-/-) mice that inhaled acrolein (1 ppm, 5 h/day for 3 days) or those exposed to acrolein in an organ bath showed diminished ACh-induced arterial relaxation more strongly than GSTP(+/+) mice. Acrolein-induced endothelial dysfunction was prevented by pretreatment of the aorta with N-acetylcysteine. These results indicate that GSTP protects against the endothelial dysfunction induced by tobacco smoke exposure and that this protection may be related to the detoxification of acrolein or other related cigarette smoke constituents.

Ovicidal activity of acrolein vapors to Indian meal moth eggs of various ages.

PubMed

Pourmirza, Ali Asghr

2007-09-01

The effect of acrolein vapors against carefully aged eggs of Indian meal moth at 27 +/- 1 and 17 +/- 1 degrees C at different dosage levels of acrolein over various exposure times was determined. Considerable variation in the susceptibility of different age groups of eggs was apparent in the fiducial limits of the LD50 values. At both temperatures and 24 h exposure period, eggs aged 1-2 day-old were more tolerant to acrolein than other age groups. In all bioassays, eggs exposed to higher dosages of acrolein developed at smaller rate. This was significant for the eggs, which were exposed to the highest dosage for 24 h. Increasing the temperature from 17 +/- 1 to 27 +/- 1 degrees C greatly increased the efficacy of acrolein. Overall, at 27 +/- 1 degrees C eggs of P. interpunctella were killed by less than one-fourth of the dosage required for control at 17 +/- 1 degrees C. Acrolein achieved 50% mortality with a dosage of 3.80 mg L(-1) in 1-2 day-old eggs at 27 +/- 1 degrees C. At this temperature hatching was retarded and greatly reduced when eggs aged 1-2 day-old were exposed to 32 mg L(-1) of acrolein for the 24 h exposure period. There was no evidence of a hatch delay longer than the time spent under vapors for eggs exposed at 17 +/- 1 or 27 +/- 1 degrees C, indicating that some development must have occurred under fumigation.

Aldose reductase (AKR1B3) regulates the accumulation of advanced glycosylation end products (AGEs) and the expression of AGE receptor (RAGE)

PubMed Central

Baba, Shahid P.; Hellmann, Jason; Srivastava, Sanjay; Bhatnagar, Aruni

2011-01-01

Diabetes results in enhanced chemical modification of proteins by advanced lipoxidation end products (ALEs) and advanced glycation end products (AGEs) precursors. These modifications have been linked to the development of several secondary diabetic complications. Our previous studies showed that aldose reductase (AR; AKR1B3) catalyzes the reduction of ALEs and AGEs precursors; however, the in vivo significance of this metabolic pathway during diabetes and obesity has not been fully assessed. Therefore we examined the role of AR in regulating ALEs and AGEs formation in murine models of diet-induced obesity and streptozotocin-induced diabetes. In comparison with wild-type (WT) and AR-null mice fed normal chow, mice fed a high-fat (HF) diet (42% kcal fat) showed increased accumulation of AGEs and protein–acrolein adducts in the plasma. AGEs and acrolein adducts were also increased in the epididymal fat of WT and AR-null mice fed a HF diet. Deletion of AR increased the accumulation of 4-hydroxy-trans-2-nonenal (HNE) protein adduct in the plasma and increased the expression of the AGE receptor (RAGE) in HF fed mice. No change in AGEs formation was observed in the kidneys of HF-fed mice. In comparison, renal tissue from AR-null mice treated with streptozotocin showed greater AGE accumulation than streptozotocin-treated WT mice. These data indicated that AR regulated the accumulation of lipid peroxidation derived aldehydes and AGEs under conditions of severe, but not mild, hyperglycemia and that deletion of AR increased RAGE-induction via mechanisms that were independent of AGEs accumulation. PMID:21276777

A single exposure to acrolein causes arrhythmogenesis, cardiac electrical dysfunction and decreased heart rate variability in hypertensive rats

EPA Science Inventory

Epidemiological studies demonstrate an association between cardiovascular morbidity, arrhythmias, and exposure to air toxicants such as acrolein. We hypothesized that a single exposure to acrolein would increase arrhythmias and cause changes in the electrocardiogram (ECG) of hype...

Structure-function relationships in the evolutionary framework of spermine oxidase.

PubMed

Cervelli, Manuela; Salvi, Daniele; Polticelli, Fabio; Amendola, Roberto; Mariottini, Paolo

2013-06-01

Spermine oxidase is a FAD-dependent enzyme that specifically oxidizes spermine, and plays a central role in the highly regulated catabolism of polyamines in vertebrates. The spermine oxidase substrate is specifically spermine, a tetramine that plays mandatory roles in several cell functions, such as DNA synthesis, cellular proliferation, modulation of ion channels function, cellular signalling, nitric oxide synthesis and inhibition of immune responses. The oxidative products of spermine oxidase activity are spermidine, H2O2 and the aldehyde 3-aminopropanal that spontaneously turns into acrolein. In this study the reconstruction of the phylogenetic relationships among spermine oxidase proteins from different vertebrate taxa allowed to infer their molecular evolutionary history, and assisted in elucidating the conservation of structural and functional properties of this enzyme family. The amino acid residues, which have been hypothesized or demonstrated to play a pivotal role in the enzymatic activity, and substrate specificity are here analysed to obtain a comprehensive and updated view of the structure-function relationships in the evolution of spermine oxidase.

IRIS TOXICOLOGICAL REVIEW AND SUMMARY DOCUMENTS FOR ACROLEIN (EXTERNAL REVIEW DRAFT)

EPA Science Inventory

Acrolein is a colorless to yellowish flammable liquid with a disagreeable, choking odor. The principal use of acrolein is as an intermediate in the synthesis of acrylic acid, which is used to make acrylates, and of DL-methionine, an essential amino acid used as an animal feed su...

Acrolein Yields in Mainstream Smoke From Commercial Cigarette and Little Cigar Tobacco Products.

PubMed

Cecil, Todd L; Brewer, Tim M; Young, Mimy; Holman, Matthew R

2017-07-01

Many carbonyls are produced from the combustion of tobacco products and many of these carbonyls are harmful or potentially harmful constituents of mainstream cigarette smoke. One carbonyl of particular interest is acrolein, which is formed from the incomplete combustion of organic matter and the most significant contributor to non-cancer respiratory effects from cigarette smoke. Sheet-wrapped cigars, also known as "little cigars," are a type of tobacco products that have not been extensively investigated in literature. This study uses standard cigarette testing protocols to determine the acrolein yields from sheet-wrapped cigars. Sheet-wrapped cigar and cigarette products were tested by derivatizing the mainstream smoke with 2,4-dinitrophenylhydrazine (DNPH) solution and then quantifying the derivatives using conventional analytical systems. The results demonstrate that sheet-wrapped cigars can be tested for acrolein yields in mainstream smoke using the same methods used for the evaluation of cigarettes. The variability in the sheet-wrapped cigars and cigarettes under the International Organization for Standardization smoking regimen is statistically similar at the 95% confidence interval; however, increased variability is observed for sheet-wrapped cigar products under the Health Canada Intense (CI) smoking regimen. The amount of acrolein released by smoking sheet-wrapped cigars can be measured using standard smoking regimen currently used for cigarettes. The sheet-wrapped cigars were determined to yield similar quantity of acrolein from commercial cigarette products using two standard smoking regimens. This article reports on the measured quantity of acrolein from 15 commercial sheet-wrapped cigars using a validated standard smoking test method that derivatizes acrolein in the mainstream smoke with DNPH solution, and uses Liquid Chromatography/Ultra-Violet Detection (LC/UV) for separation and detection. These acrolein yields were similar to the levels found in the smoke from 35 commercial cigarette products measured in the same manner. Although sheet-wrapped cigar data were slightly more variable than those found for the cigarette data, this article reports that the production of acrolein is similar to cigarettes. The results demonstrate that sheet-wrapped cigars can be tested for acrolein yields in mainstream smoke using the same methods used for the evaluation of cigarettes. Published by Oxford University Press on behalf of the Society for Research on Nicotine and Tobacco 2017. This work is written by (a) US Government employee(s) and is in the public domain in the US.

POTENTIATION OF PULMONARY REFLEX RESPONSE TO CAPSAICIN 24 HOURS FOLLOWING WHOLE-BODY ACROLEIN EXPOSURE IS MEDIATED BY TRPV1

EPA Science Inventory

Pulmonary C-fibers are stimulated by irritant air pollutants producing apnea, bronchospasm, and decrease in HR. C-fiber chemoreflex activation is mediated by TRPV1 and release of substance P. While acrolein has been shown to stimulate C-fibers, the persistence of acrolein effect...

TRPA1 mediates changes in heart rate variability and cardiac mechanical function in mice exposed to acrolein

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurhanewicz, Nicole

Short-term exposure to ambient air pollution is linked with adverse cardiovascular effects. While previous research focused primarily on particulate matter-induced responses, gaseous air pollutants also contribute to cause short-term cardiovascular effects. Mechanisms underlying such effects have not been adequately described, however the immediate nature of the response suggests involvement of irritant neural activation and downstream autonomic dysfunction. Thus, this study examines the role of TRPA1, an irritant sensory receptor found in the airways, in the cardiac response of mice to acrolein and ozone. Conscious unrestrained wild-type C57BL/6 (WT) and TRPA1 knockout (KO) mice implanted with radiotelemeters were exposed once tomore » 3 ppm acrolein, 0.3 ppm ozone, or filtered air. Heart rate (HR) and electrocardiogram (ECG) were recorded continuously before, during and after exposure. Analysis of ECG morphology, incidence of arrhythmia and heart rate variability (HRV) were performed. Cardiac mechanical function was assessed using a Langendorff perfusion preparation 24 h post-exposure. Acrolein exposure increased HRV independent of HR, as well as incidence of arrhythmia. Acrolein also increased left ventricular developed pressure in WT mice at 24 h post-exposure. Ozone did not produce any changes in cardiac function. Neither gas produced ECG effects, changes in HRV, arrhythmogenesis, or mechanical function in KO mice. These data demonstrate that a single exposure to acrolein causes cardiac dysfunction through TRPA1 activation and autonomic imbalance characterized by a shift toward parasympathetic modulation. Furthermore, it is clear from the lack of ozone effects that although gaseous irritants are capable of eliciting immediate cardiac changes, gas concentration and properties play important roles. - Highlights: • Acute acrolein exposure causes autonomic imbalance and altered CV function in mice. • TRPA1 mediates acrolein-induced autonomic nervous system cardiac effects. • Sensory irritation contributes to acrolein-induced cardiac arrhythmia & dysfunction.« less

Cooking-related PM2.5 and acrolein measured in grocery stores and comparison with other retail types.

PubMed

Chan, W R; Sidheswaran, M; Sullivan, D P; Cohn, S; Fisk, W J

2016-06-01

We measured particulate matter (PM), acrolein, and other indoor air contaminants in eight visits to grocery stores in California. Retail stores of other types (hardware, furniture, and apparel) were also sampled on additional visits. Based on tracer gas decay data, most stores had adequate ventilation according to minimum ventilation rate standards. Grocery stores had significantly higher concentrations of acrolein, fine and ultrafine PM, compared to other retail stores, likely attributable to cooking. Indoor concentrations of PM2.5 and acrolein exceeded health guidelines in all tested grocery stores. Acrolein emission rates to indoors in grocery stores had a mean estimate about 30 times higher than in other retail store types. About 80% of the indoor PM2.5 measured in grocery stores was emitted indoors, compared to only 20% for the other retail store types. Calculations suggest a substantial increase in outdoor air ventilation rate by a factor of three from current level is needed to reduce indoor acrolein concentrations. Alternatively, acrolein emission to indoors needs to be reduced 70% by better capturing of cooking exhaust. To maintain indoor PM2.5 below the California annual ambient standard of 12 μg/m(3) , grocery stores need to use air filters with an efficiency rating higher than the MERV 8 air filters commonly used today. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Notes from the field: Acute pesticide-related illness resulting from occupational exposure to acrolein - Washington and California, 1993-2009.

PubMed

2013-04-26

Acrolein is an aquatic herbicide used in the western United States to prevent impaired water flow in irrigation canals. Despite its toxicity, few cases of acrolein-related illness have been reported in the literature. On August 15, 2012, an irrigation district notified the Washington State Department of Labor & Industries (L&I) of acrolein-related illness in one of its pesticide applicators. L&I inspected the site and interviewed the exposed worker, coworkers, and employer. The Washington State Department of Health assisted by obtaining medical records, interviewing the patient and hospital staff, and reviewing information obtained from L&I. To look for additional cases, CDC reviewed data from the SENSOR-Pesticides program* and the California Department of Pesticide Regulation for 1993-2009, the most recent years of data availability, and identified seven additional cases of acute acrolein-related illness.

Seasonal evaluation of disinfection by-products throughout two full-scale drinking water treatment plants.

PubMed

Zhong, Xin; Cui, Chongwei; Yu, Shuili

2017-07-01

Carbonyl compounds can occur alpha-hydrogens or beta-diketones substitution reactions with disinfectants contributed to halogenated by-products formation. The objective of this research was to study the occurrence and fate of carbonyl compounds as ozonation by-products at two full-scale drinking water treatment plants (DWTPs) using different disinfectants for one year. The quality of the raw water used in both plants was varied according to the season. The higher carbonyl compounds concentrations were found in raw water in spring. Up to 15 (as the sum of both DWTPs) of the 24 carbonyl compounds selected for this work were found after disinfection. The dominant carbonyl compounds were formaldehyde, glyoxal, methyl-glyoxal, fumaric, benzoic, protocatechuic and 3-hydroxybenzoic acid at both DWTPs. In the following steps in each treatment plant, the concentration patterns of these carbonyl compounds differed depending on the type of disinfectant applied. Benzaldehyde was the only aromatic aldehyde detected after oxidation with ozone in spring. As compared with DWTP 1, five new carbonyl compounds were formed (crotonaldehyde, benzaldehyde, formic, oxalic and malonic acid) disinfection by ozone, and the levels of the carbonyl compounds increased. In addition, pre-ozonation (PO) and main ozonation (OZ) increased the levels of carbonyl compounds, however coagulation/flocculation (CF), sand filtration (SF) and granular activated carbon filtration (GAC) decreased the levels of carbonyl compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Vocal fold ion transport and mucin expression following acrolein exposure

PubMed Central

Levendoski, Elizabeth Erickson; Sivasankar, M. Preeti

2014-01-01

The vocal fold epithelium is exposed to inhaled particulates including pollutants during breathing in everyday environments. Yet, our understanding of the effects of pollutants on vocal fold epithelial function is extremely limited. The objective of this study was to investigate the effect of the pollutant acrolein on two vocal fold epithelial mechanisms: ion transport and mucin synthesis. These mechanisms were chosen as each plays a critical role in vocal defense and in maintaining surface hydration which is necessary for optimal voice production. Healthy, native porcine vocal folds (N=85) were excised and exposed to an acrolein or sham challenge. A 60 minute acrolein, but not sham challenge significantly reduced ion transport and inhibited cyclic adenosine monophosphate-dependent increases in ion transport. Decreases in ion transport were associated with reduced sodium absorption. Within the same timeline, no significant acrolein-induced changes in mucin gene or protein expression were observed. These results improve our understanding of the effects of acrolein on key vocal fold epithelial functions and inform the development of future investigations that seek to elucidate the impact of a wide range of pollutant exposures on vocal fold health. PMID:24648011

Methoxyflurane enhances allyl alcohol hepatotoxicity in rats. Possible involvement of increased acrolein formation.

PubMed

Kershaw, W C; Barsotti, D A; Leonard, T B; Dent, J G; Lage, G L

1989-01-01

The effect of methoxyflurane anesthesia on allyl alcohol-induced hepatotoxicity and the metabolism of allyl alcohol was studied in male rats. Hepatotoxicity was assessed by the measurement of serum alanine aminotransferase activity and histopathological examination. Allyl alcohol-induced hepatotoxicity was enhanced when allyl alcohol (32 mg/kg) was administered 4 hr before or up to 8 days after a single 10-min exposure to methoxyflurane vapors. The possibility that methoxyflurane increases alcohol dehydrogenase-dependent oxidation of allyl alcohol to acrolein, the proposed toxic metabolite, was evaluated by measuring the rate of acrolein formation in the presence of allyl alcohol and liver cytosol. The effect of methoxyflurane on alcohol dehydrogenase activity in liver cytosol was also assessed by measuring the rate of NAD+ utilization in the presence of ethyl alcohol or allyl alcohol. Alcohol dehydrogenase activity and rate of acrolein formation were elevated in methoxyflurane-pretreated rats. The results suggest that a modest increase in alcohol dehydrogenase activity and rate of acrolein formation markedly enhances allyl alcohol-induced hepatotoxicity.

Respiratory Effects and Systemic Stress Response Following ...

EPA Pesticide Factsheets

Previous studies have demonstrated that exposure to ozone, a pulmonary irritant, causes myriad systemic metabolic and pulmonary effects that are attributed to neuronal and hypothalamus-pituitary-adrenal (HPA) axis activation, which are exacerbated in metabolically-impaired models. In order to elucidate the systemic consequences and the contribution of the HPA axis in mediating metabolic and respiratory effects of acrolein, a sensory irritant, we examined pulmonary, nasal, and systemic effects in rats following exposure. Male, 10 week old Wistar and Goto Kakizaki (GK) rats, a non-obese type II diabetic Wistar-derived model, were exposed to 0, 2 or 4 ppm acrolein, 4h/day for 1 or 2 days. Acrolein exposure at 4 ppm significantly increased pulmonary and nasal damage in both strains as demonstrated by increased inspiratory and expiratory times indicating labored breathing, elevated biomarkers of injury, and neutrophilic inflammation. Overall, at both time points acrolein exposure caused noticeably more damage in the nasal passages as opposed to the lung with vascular protein leakage occurring only in the nose. Acrolein exposure (4 ppm) also led to metabolic impairment by inducing hyperglycemia and glucose intolerance (GK>Wistar) as indicated by glucose tolerance testing. In addition, serum total cholesterol (GKs only), LDL cholesterol (both strains), and free fatty acids (GK>Wistar) levels increased; however, no acrolein-induced changes were noted in branched-c

Protein alkylation, transcriptional responses and cytochrome c release during acrolein toxicity in A549 cells: influence of nucleophilic culture media constituents.

PubMed

Thompson, Colin A; Burcham, Philip C

2008-06-01

Acrolein is a toxic combustion product that elicits apoptotic and/or necrotic cell death depending on the conditions under which exposure occurs. As a strong electrophile, side-reactions with nucleophilic media constituents seem likely to accompany study of its toxicity in vitro, but these reactions are poorly characterized. We have thus examined the effect of media composition on the toxicity of acrolein in A549 cells. Cells were exposed to acrolein in either Dulbecco's buffered saline (DBS) or F12 supplemented with various concentrations of fetal bovine serum. Cell viability was assessed using the MTT assay, while heme oxygenase-1 (HO-1) and cytoplasmic cytochrome c were measured as respective markers of transcriptional response and apoptosis. Protein damage was evaluated using the protein carbonyl assay. Compared to F12 media (with or without serum), maximal cell death as evaluated using the MTT assay, as well as adduction of intracellular proteins, occurred when cells were exposed to acrolein in DBS. In contrast, cytochrome c release was maximal in cells exposed to acrolein in serum-containing F12, conditions which inhibited protein modification and overt cell death. These findings highlight the need for careful attention to experimental conditions when conducting in vitro toxicological studies of reactive substances.

[Changes of CD(4)(+) Foxp3+ regulatory T cells and CD(4)(+)IL-17+T cells in acrolein exposure rats].

PubMed

Wei, Ming; Tu, Ling; Liang, Yinghong; Li, Jia; Gong, Yanjie; Zhang, Yihua; Yang, Lu

2015-09-01

To evaluate the changes of CD(4)(+) IL-17+T (Th17) and CD(4)(+)Foxp3+regulatory T (Treg) cells in peripheral blood and bronchoalveolar lavage fluid (BALF) , and therefore to explore the role of Th17 and Treg in acrolein exposure airway inflammation in rats. Forty male Wistar rats were randomly divided into 4 groups: a 2 wk acrolein exposure group, a 4 wk acrolein exposure group, a 2 wk control group and a 4 wk control group (n=10 each). Cells in BALF were collected and analyzed by absolute and differential cell counts.IL-17 and IL-6 levels in serum and BALF were tested by enzyme linked immunosorbent assay (ELISA). The proportion of CD(4)(+)IL-17+T and CD(4)(+) Foxp3+Treg in peripheral blood and BALF were determined by flow cytometry.The mRNA expressions of IL-17 and Foxp3 were measured by real-time PCR. Comparisons of the data between different groups were performed using one-way ANOVA, and SNK and Games-Howell test were used for comparison between 2 groups. Levels of IL-17 were remarkable increased in the 2 wk acrolein exposure group and the 4 wk acrolein exposure group in serum [(52.64 ± 1.89) ng/L, (76.73 ± 5.57) ng/L], and BALF [(79.07 ± 5.67) ng/L, (96.61 ± 6.44) ng/L] compared with the 2 wk control group [(40.05 ± 3.12) ng/L, (56.75 ± 4.37) ng/L] and the 4 wk control group [(38.75 ± 3.23) ng/L, (53.27 ± 4.48) ng/L], all P<0.01. IL-6 was increased in the 2 wk and the 4 wk acrolein exposure group [ (33.28 ± 2.27) ng/L, (46.24 ± 3.16) ng/L] compared with the 2 wk and the 4 wk control group [ (16.37 ± 1.49) ng/L, (17.02 ± 1.43) ng/L] in BALF.Ratio of Th17 was higher in the 2 wk and the 4 wk acrolein exposure groups in peripheral blood (1.82 ± 0.18) %, (3.75 ± 0.48) % and BALF [(7.23 ± 0.27) %, (8.12 ± 0.38) %] compared with the 2 wk [(0.96 ± 0.07) %, (5.64 ± 0.63) %] and the 4 wk control group [(1.01 ± 0.08) %, (5.86 ± 0.57) %]. Ratio of Treg in BALF was higher in the acrolein exposure groups [ (8.83 ± 0.52) %, (12.05 ± 0.74) %] compared with the control groups [(4.37 ± 0.27) %, (5.01 ± 0.37) %]. The level of IL-17 mRNA was increased in the 2 wk and the 4 wk acrolein exposure group in peripheral blood [(25.78 ± 2.31), (34.69 ± 2.01) ] and in BALF [(23.04 ± 1.78), (34.56 ± 3.12)] compared with the 2 wk [(11.04 ± 2.53), (11.08 ± 2.05)] and the 4 wk [(12.03 ± 2.34), (12.69 ± 2.69)] control groups. Foxp3 mRNA was increased in the acrolein exposure groups [ (26.37 ± 3.24), (33.19 ± 2.98)] (24.4 ± 2.7), (30.3 ± 2.7) compared with the control groups [(12.37 ± 2.56), (13.12 ± 3.08)]. Th17 in acrolein exposure groups was positively correlated with counts of total cells and macrophages (r=0.5126, 0.5437, all P<0.01). A changed expression of Th17 and Treg cells and an vary of inflammatory cytokines were evident in airway inflammation of acrolein exposed rats, suggesting that Treg was involved in the immunological regulation and Th17 was associated with the persistent inflammation in acrolein induced airway inflammation in rats.

Estimating Risk from Ambient Concentrations of Acrolein across the United States

PubMed Central

Woodruff, Tracey J.; Wells, Ellen M.; Holt, Elizabeth W.; Burgin, Deborah E.; Axelrad, Daniel A.

2007-01-01

Background Estimated ambient concentrations of acrolein, a hazardous air pollutant, are greater than the U.S. Environmental Protection Agency (EPA) reference concentration throughout the United States, making it a concern for human health. However, there is no method for assessing the extent of risk under the U.S. EPA noncancer risk assessment framework. Objectives We estimated excess risks from ambient concentrations of acrolein based on dose–response modeling of a study in rats with a relationship between acrolein and residual volume/total lung capacity ratio (RV/TLC) and specific compliance (sCL), markers for altered lung function. Methods Based on existing literature, we defined values above the 90th percentile for controls as “adverse.” We estimated the increase over baseline response that would occur in the human population from estimated ambient concentrations of acrolein, taken from the U.S. EPA’s National-Scale Air Toxics Assessment for 1999, after standard animal-to-human conversions and extrapolating to doses below the experimental data. Results The estimated median additional number of adverse sCL outcomes across the United States was approximately 2.5 cases per 1,000 people. The estimated range of additional outcomes from the 5th to the 95th percentile of acrolein concentration levels across census tracts was 0.28–14 cases per 1,000. For RV/TLC, the median additional outcome was 0.002 per 1,000, and the additional outcome at the 95th percentile was 0.13 per 1,000. Conclusions Although there are uncertainties in estimating human risks from animal data, this analysis demonstrates a method for estimating health risks for noncancer effects and suggests that acrolein could be associated with decreased respiratory function in the United States. PMID:17431491

Evaluation of dementia by acrolein, amyloid-β and creatinine.

PubMed

Igarashi, Kazuei; Yoshida, Madoka; Waragai, Masaaki; Kashiwagi, Keiko

2015-10-23

Plasma, urine and cerebrospinal fluid (CSF) were examined for biochemical markers of dementia. Protein-conjugated acrolein (PC-Acro) and the amyloid-β (Aβ)40/42 ratio in plasma can be used to detect mild cognitive impairment (MCI) and Alzheimer's disease (AD). In plasma, PC-Acro and the Aβ40/42 ratio in MCI and AD were significantly higher relative to non-demented subjects. Furthermore, urine acrolein metabolite, 3-hydroxypropyl mercapturic acid (3-HPMA)/creatinine (Cre) and amino acid-conjugated acrolein (AC-Acro)/Cre in AD were significantly lower than MCI. It was also shown that reduced urine 3-HPMA/Cre correlated with increased plasma Aβ40/42 ratio in dementia. The Aβ40/PC-Acro ratio in CSF, together with Aβ40 and Aβ40/42 ratio, was lower in AD than MCI. Increased plasma PC-Acro and Aβ40/42 ratio and decreased urine 3-HPMA/Cre correlated with cognitive ability (MMSE). These results indicate that the measurements of acrolein derivatives together with Aβ and Cre in biologic fluids is useful to estimate severity of dementia. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of Catalyst Acid/Base Properties in Acrolein Production by Oxidative Coupling of Ethanol and Methanol.

PubMed

Lilić, Aleksandra; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

2017-05-09

Oxidative coupling of methanol and ethanol represents a new route to produce acrolein. In this work, the overall reaction was decoupled in two steps, the oxidation and the aldolization, by using two consecutive reactors to investigate the role of the acid/base properties of silica-supported oxide catalysts. The oxidation of a mixture of methanol and ethanol to formaldehyde and acetaldehyde was performed over a FeMoO x catalyst, and then the product mixture was transferred without intermediate separation to a second reactor, in which the aldol condensation and dehydration to acrolein were performed over the supported oxides. The impact of the acid/base properties on the selectivity towards acrolein was investigated under oxidizing conditions for the first time. The acid/base properties of the catalysts were investigated by NH 3 -, SO 2 -, and methanol-adsorption microcalorimetry. A MgO/SiO 2 catalyst was the most active in acrolein production owing to an appropriate ratio of basic to acidic sites. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A method of detecting carbonyl compounds in tree leaves in China.

PubMed

Huang, Juan; Feng, Yanli; Fu, Jiamo; Sheng, Guoying

2010-06-01

Carbonyl compounds have been paid more and more attention because some carbonyl species have been proven to be carcinogenic or a risk for human health. Plant leaves are both an important emission source and an important sink of carbonyl compounds. But the research on carbonyl compounds from plant leaves is very scarce. In order to make an approach to the emission mechanism of plant leaves, a new method was established to extract carbonyl compounds from fresh plant leaves. The procedure combining derivatization with ultrasonication was developed for the fast extraction of carbonyl compounds from tree leaves. Fresh leaves (< 0.01 g) were minced and ultrasonicated in acidic 2,4-dinitrophenylhydrazine (DNPH)-acetonitrile solution for 30 min and then holding 30 min to allow aldehydes and ketones in leaves to react completely with DNPH. The extraction process was performed under room temperature and only took 60 min. The advantages of this method were very little sample preparation, requiring short treatment time and usual equipment. Four greening trees, i.e., camphor tree (Cinnamomum camphora), sweet olive (Osmanthus fragrans), cedar (Cedrus deodara), and dawn redwood (Metasequoia glyptostroboides), were selected and extracted by this method. Seven carbonyl compounds, including formaldehyde, acetaldehyde, acetone, acrolein, p-tolualdehyde, m/o-tolualdehyde, and hexaldehyde were determined and quantified. The most common carbonyl species of the four tree leaves were formaldehyde, acrolein, and m/o-tolualdehyde. They accounted for 67.3% in cedar, 50.8% in sweet olive, 45.8% in dawn redwood, and 44.6% in camphor tree, respectively. Camphor tree had the highest leaf level of m/o-tolualdehyde with 15.0 +/- 3.4 microg g(-1)(fresh leaf weight), which indicated that camphor tree may be a bioindicator of the level of tolualdehyde or xylene in the atmosphere. By analyzing carbonyl compounds from different tree leaves, it is not only helpful for further studying the relationship between sink and emission of carbonyls from plants, but also helpful for exploring optimum plant population in urban greening.

Method development study for APR cartridge evaluation in fire overhaul exposures.

PubMed

Anthony, T Renée; Joggerst, Philip; James, Leonard; Burgess, Jefferey L; Leonard, Stephen S; Shogren, Elizabeth S

2007-11-01

In the US, firefighters do not typically wear respiratory protection during overhaul activities, although fitting multi-gas or chemical, biological, radiological and nuclear cartridges to supplied air respirator facepieces has been proposed to reduce exposures. This work developed a method to evaluate the effectiveness of respirator cartridges in smoke that represents overhaul exposures to residential fires. Chamber and penetration concentrations were measured for 91 contaminants, including aldehydes, polynuclear aromatic hydrocarbons, hydrocarbons and methyl isothiocyanate, along with total and respirable particulates. These laboratory tests generated concentrations in the range of field-reported exposures from overhaul activities. With limited tests, no styrene, benzene, acrolein or particulates were detected in air filtered by the respirator cartridge, yet other compounds were detected penetrating the respirator. Because of the complexity of smoke, an exposure index was determined for challenge and filtered air to determine the relative risk of the aggregate exposure to respiratory irritants. The primary contributors to the irritant exposure index in air filtered by the respirator were formaldehyde and acetaldehyde, with total hydrocarbons contributing only 1% to the irritant index. Respirator cartridges were adequate to minimize firefighter exposures to aggregate respiratory irritants if the American Conference of Governmental Industrial Hygienists ceiling limit for formaldehyde is used (0.3 ppm) but not if National Institute for Occupational Safety and Health Recommended Exposure Limit (NIOSH REL) (0.1 ppm) is used, where three of five concentrations in filtered air exceeded the NIOSH REL. Respirator certification allows 1 ppm of formaldehyde to pass through it when challenged at 100 ppm, which may not adequately protect workers to current short-term exposure/ceiling limits. The method developed here recommends specific contaminants to measure in future work (formaldehyde, acrolein, acetaldehyde, naphthalene, benzene, total hydrocarbons as toluene and particulate mass) along with inclusion of additional irritant gases and hydrogen cyanide to fully evaluate whether air-purifying respirators reduce exposures to the aggregate gases/vapors present in overhaul activities.

Assessment of indoor air quality in office buildings across Europe - The OFFICAIR study.

PubMed

Mandin, Corinne; Trantallidi, Marilena; Cattaneo, Andrea; Canha, Nuno; Mihucz, Victor G; Szigeti, Tamás; Mabilia, Rosanna; Perreca, Erica; Spinazzè, Andrea; Fossati, Serena; De Kluizenaar, Yvonne; Cornelissen, Eric; Sakellaris, Ioannis; Saraga, Dikaia; Hänninen, Otto; De Oliveira Fernandes, Eduardo; Ventura, Gabriela; Wolkoff, Peder; Carrer, Paolo; Bartzis, John

2017-02-01

The European project OFFICAIR aimed to broaden the existing knowledge regarding indoor air quality (IAQ) in modern office buildings, i.e., recently built or refurbished buildings. Thirty-seven office buildings participated in the summer campaign (2012), and thirty-five participated in the winter campaign (2012-2013). Four rooms were investigated per building. The target pollutants were twelve volatile organic compounds, seven aldehydes, ozone, nitrogen dioxide and particulate matter with aerodynamic diameter <2.5μm (PM 2.5 ). Compared to other studies in office buildings, the benzene, toluene, ethylbenzene, and xylene concentrations were lower in OFFICAIR buildings, while the α-pinene and d-limonene concentrations were higher, and the aldehyde, nitrogen dioxide and PM 2.5 concentrations were of the same order of magnitude. When comparing summer and winter, significantly higher concentrations were measured in summer for formaldehyde and ozone, and in winter for benzene, α-pinene, d-limonene, and nitrogen dioxide. The terpene and 2-ethylhexanol concentrations showed heterogeneity within buildings regardless of the season. Considering the average of the summer and winter concentrations, the acetaldehyde and hexanal concentrations tended to increase by 4-5% on average with every floor level increase, and the nitrogen dioxide concentration tended to decrease by 3% on average with every floor level increase. A preliminary evaluation of IAQ in terms of potential irritative and respiratory health effects was performed. The 5-day median and maximum indoor air concentrations of formaldehyde and ozone did not exceed their respective WHO air quality guidelines, and those of acrolein, α-pinene, and d-limonene were lower than their estimated thresholds for irritative and respiratory effects. PM 2.5 indoor concentrations were higher than the 24-h and annual WHO ambient air quality guidelines. Copyright © 2016 Elsevier B.V. All rights reserved.

Human aldo-keto reductases 1B1 and 1B10: a comparative study on their enzyme activity toward electrophilic carbonyl compounds.

PubMed

Shen, Yi; Zhong, Linlin; Johnson, Stephen; Cao, Deliang

2011-05-30

Aldo-keto reductase family 1 member B1 (AKR1B1, 1B1 in brief) and aldo-keto reductase family 1 member B10 (AKR1B10, 1B10 in brief) are two proteins with high similarities in their amino acid sequences, stereo structures, and substrate specificity. However, these two proteins exhibit distinct tissue distributions; 1B10 is primarily expressed in the gastrointestinal tract and adrenal gland, whereas 1B1 is ubiquitously present in all tissues/organs, suggesting their difference in biological functions. This study evaluated in parallel the enzyme activity of 1B1 and 1B10 toward alpha, beta-unsaturated carbonyl compounds with cellular and dietary origins, including acrolein, crotonaldehyde, 4-hydroxynonenal, trans-2-hexenal, and trans-2,4-hexadienal. Our results showed that 1B10 had much better enzyme activity and turnover rates toward these chemicals than 1B1. By detecting the enzymatic products using high-performance liquid chromatography, we measured their activity to carbonyl compounds at low concentrations. Our data showed that 1B10 efficiently reduced the tested carbonyl compounds at physiological levels, but 1B1 was less effective. Ectopically expressed 1B10 in 293T cells effectively eliminated 4-hydroxynonenal at 5 μM by reducing to 1,4-dihydroxynonene, whereas endogenously expressed 1B1 did not. The 1B1 and 1B10 both showed enzyme activity to glutathione-conjugated carbonyl compounds, but 1B1 appeared more active in general. Together our data suggests that 1B10 is more effectual in eliminating free electrophilic carbonyl compounds, but 1B1 seems more important in the further detoxification of glutathione-conjugated carbonyl compounds. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Magnolol protects against oxidative stress-mediated neural cell damage by modulating mitochondrial dysfunction and PI3K/Akt signaling.

PubMed

Dong, Liqun; Zhou, Shu; Yang, Xiaohua; Chen, Qianming; He, Yang; Huang, Wen

2013-07-01

Magnolol, an orally available compound from Magnolia officinalis used widely in traditional herbal medicine against a variety of neuronal diseases, possesses potent antioxidant properties and protects the brain against oxidative damage. The aim of the work is to examine the protective mechanisms of magnolol on human neuroblastoma SH-SY5Y cells against apoptosis induced by the neurotoxin acrolein, which can cause neurodegenerative disorders by inducing oxidative stress. By investigating the effect of magnolol on neural cell damage induced by the neurotoxin acrolein, we found that magnolol pretreatment significantly attenuated acrolein-induced oxidative stress through inhibiting reactive oxygen species accumulation caused by intracellular glutathione depletion and nicotinamide adenine dinucleotide phosphate oxidase activation. We next examined the signaling cascade(s) involved in magnolol-mediated antiapoptotic effects. The results showed that acrolein induced SH-SY5Y cell apoptosis by activating mitochondria/caspase and MEK/ERK signaling pathways. Our findings provide the first evidence that magnolol protects SH-SY5Y cells against acrolein-induced oxidative stress and prolongs SH-SY5Y cell survival through regulating JNK/mitochondria/caspase, PI3K/MEK/ERK, and PI3K/Akt/FoxO1 signaling pathways.

Aggravation of brain infarction through an increase in acrolein production and a decrease in glutathione with aging.

PubMed

Uemura, Takeshi; Watanabe, Kenta; Ishibashi, Misaki; Saiki, Ryotaro; Kuni, Kyoshiro; Nishimura, Kazuhiro; Toida, Toshihiko; Kashiwagi, Keiko; Igarashi, Kazuei

2016-04-29

We previously reported that tissue damage during brain infarction was mainly caused by inactivation of proteins by acrolein. This time, it was tested why brain infarction increases in parallel with aging. A mouse model of photochemically induced thrombosis (PIT) was studied using 2, 6, and 12 month-old female C57BL/6 mice. The size of brain infarction in the mouse PIT model increased with aging. The volume of brain infarction in 12 month-old mice was approximately 2-fold larger than that in 2 month-old mice. The larger brain infarction in 12 month-old mice was due to an increase in acrolein based on an increase in the activity of spermine oxidase, together with a decrease in glutathione (GSH), a major acrolein-detoxifying compound in cells, based on the decrease in one of the subunits of glutathione biosynthesizing enzymes, γ-glutamylcysteine ligase modifier subunit, with aging. The results indicate that aggravation of brain infarction with aging was mainly due to the increase in acrolein production and the decrease in GSH in brain. Copyright © 2016 Elsevier Inc. All rights reserved.

Measurement of acrolein and 1,3-butadiene in a single puff of cigarette smoke using lead-salt tunable diode laser infrared spectroscopy.

PubMed

Thweatt, W Dave; Harward, Charles N; Parrish, Milton E

2007-05-01

Acrolein and 1,3-butadiene in cigarette smoke generally are measured using two separate analytical methods, a carbonyl derivative HPLC method for acrolein and a volatile organic compound (VOC) GC/MS method for 1,3-butadiene. However, a single analytical method having improved sensitivity and real-time per puff measurement will offer more specific information for evaluating experimental carbon filtered cigarettes designed to reduce the smoke deliveries of these constituents. This paper describes an infrared technique using two lead-salt tunable diode lasers (TDLs) operating with liquid nitrogen cooling with emissions at 958.8 cm(-1) and 891.0 cm(-1) respectively for the simultaneous measurement of acrolein and 1,3-butadiene, respectively, in each puff of mainstream cigarette smoke in real time. The dual TDL system uses a 3.1l volume, 100 m astigmatic multiple pass absorption gas cell. Quantitation is based on a spectral fit that uses previously determined infrared molecular line parameters generated in our laboratory, including line positions, line strengths and nitrogen-broadened half-widths for these species. Since acrolein and ethylene absorption lines overlap and 1,3-butadiene, ethylene and propylene absorption lines overlap, the per puff deliveries of ethylene and propylene were determined since their overlapping absorption lines must be taken into account by the spectral fit. The acrolein and 1,3-butadiene total cigarette deliveries for the 1R5F Kentucky Reference cigarette were in agreement with the HPLC and GC/MS methods, respectively. The limit of detection (LOD) for 1,3-butadiene and acrolein was 4 ng/puff and 24 ng/puff, respectively, which is more than adequate to determine at which puff they break through the carbon filter. The retention and breakthrough behavior for the two primary smoke constituents depend on the cigarette design and characteristics of the carbon filter being evaluated.

Measurement of acrolein and 1,3-butadiene in a single puff of cigarette smoke using lead-salt tunable diode laser infrared spectroscopy

NASA Astrophysics Data System (ADS)

Thweatt, W. Dave; Harward, Charles N., Sr.; Parrish, Milton E.

2007-05-01

Acrolein and 1,3-butadiene in cigarette smoke generally are measured using two separate analytical methods, a carbonyl derivative HPLC method for acrolein and a volatile organic compound (VOC) GC/MS method for 1,3-butadiene. However, a single analytical method having improved sensitivity and real-time per puff measurement will offer more specific information for evaluating experimental carbon filtered cigarettes designed to reduce the smoke deliveries of these constituents. This paper describes an infrared technique using two lead-salt tunable diode lasers (TDLs) operating with liquid nitrogen cooling with emissions at 958.8 cm -1 and 891.0 cm -1 respectively for the simultaneous measurement of acrolein and 1,3-butadiene, respectively, in each puff of mainstream cigarette smoke in real time. The dual TDL system uses a 3.1 l volume, 100 m astigmatic multiple pass absorption gas cell. Quantitation is based on a spectral fit that uses previously determined infrared molecular line parameters generated in our laboratory, including line positions, line strengths and nitrogen-broadened half-widths for these species. Since acrolein and ethylene absorption lines overlap and 1,3-butadiene, ethylene and propylene absorption lines overlap, the per puff deliveries of ethylene and propylene were determined since their overlapping absorption lines must be taken into account by the spectral fit. The acrolein and 1,3-butadiene total cigarette deliveries for the 1R5F Kentucky Reference cigarette were in agreement with the HPLC and GC/MS methods, respectively. The limit of detection (LOD) for 1,3-butadiene and acrolein was 4 ng/puff and 24 ng/puff, respectively, which is more than adequate to determine at which puff they break through the carbon filter. The retention and breakthrough behavior for the two primary smoke constituents depend on the cigarette design and characteristics of the carbon filter being evaluated.

Spectators Control Selectivity in Surface Chemistry: Acrolein Partial Hydrogenation Over Pd

PubMed Central

2015-01-01

We present a mechanistic study on selective hydrogenation of acrolein over model Pd surfaces—both single crystal Pd(111) and Pd nanoparticles supported on a model oxide support. We show for the first time that selective hydrogenation of the C=O bond in acrolein to form an unsaturated alcohol is possible over Pd(111) with nearly 100% selectivity. However, this process requires a very distinct modification of the Pd(111) surface with an overlayer of oxopropyl spectator species that are formed from acrolein during the initial stages of reaction and turn the metal surface selective toward propenol formation. By applying pulsed multimolecular beam experiments and in situ infrared reflection–absorption spectroscopy, we identified the chemical nature of the spectator and the reactive surface intermediate (propenoxy species) and experimentally followed the simultaneous evolution of the reactive intermediate on the surface and formation of the product in the gas phase. PMID:26481220

Synthesis of nucleosides and oligonucleotides containing adducts of acrolein and vinyl chloride.

PubMed

Nechev, L V; Harris, C M; Harris, T M

2000-05-01

Vinyl chloride and acrolein are important industrial chemicals. Both form DNA adducts, vinyl chloride after enzymatic oxidation to chlorooxirane and acrolein by direct reaction. Reaction at the N(2) position of guanine is a major pathway. The resulting 2-oxoethyl and 3-oxopropyl adducts cyclize spontaneously to hydroxyethano and hydroxypropano derivatives, respectively. The two cyclic adducts have been detected in DNA exposed to these mutagens. A new method has been developed for the synthesis of deoxyguanosine adducts of chlorooxirane and acrolein, as well as oligonucleotides containing these adducts. Reaction of O(6)-[(trimethylsilyl)ethyl]-2-fluoro-2'-deoxyinosine with the appropriate aminodiol followed by oxidative cleavage of the diol with NaIO(4) gave the adducts in excellent yields. Reaction of oligonucleotides containing the halonucleoside with the aminodiols followed by NaIO(4) efficiently created the nucleosides in the oligonucleotides. Deoxyadenosine adducts were created similarly using 6-chloropurine 9-(2'-deoxyriboside).

Acrolein

Integrated Risk Information System (IRIS)

EPA / 635 / R - 03 / 003 TOXICOLOGICAL REVIEW OF ACROLEIN ( CAS No . 107 - 02 - 8 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) May 2003 US Environmental Protection Agency Washington , DC DISCLAIMER This document has been reviewed in accordance with U.S . Env

Nanofilter platform based on functionalized carbon nanotubes for adsorption and elimination of Acrolein, a toxicant in cigarette smoke

NASA Astrophysics Data System (ADS)

Yoosefian, Mehdi; Pakpour, Atef; Etminan, Nazanin

2018-06-01

This paper discusses the use of carboxylated single-walled carbon nanotube as a general nanofilter platform for the removal of acrolein carcinogen from cigarette smoke. The analyses carried out in the detailed study of the electronic and structural effects of the adsorption of acrolein onto COOH loaded on single-walled carbon nanotube under the density functional theory framework. The results of Bader theory of atoms in molecules, natural bond orbital, molecular potential electron surface and density of state confirm the potential application of the suggested nanofilter platform.

Respiratory Effects and Systemic Stress Response Following ...

EPA Pesticide Factsheets

Previous studies have demonstrated that exposure to the pulmonary irritant ozone causes myriad systemic metabolic and pulmonary effects attributed to sympathetic and hypothalamus-pituitary-adrenal (HPA) axis activation, which are exacerbated in metabolically impaired models. We examined respiratory and systemic effects following exposure to a sensory irritant acrolein to elucidate the systemic and pulmonary consequences in healthy and diabetic rat models. Male Wistar and Goto Kakizaki (GK) rats, a nonobese type II diabetic Wistar-derived model, were exposed by inhalation to 0, 2, or 4 ppm acrolein, 4 h/d for 1 or 2 days. Exposure at 4 ppm significantly increased pulmonary and nasal inflammation in both strains with vascular protein leakage occurring only in the nose. Acrolein exposure (4 ppm) also caused metabolic impairment by inducing hyperglycemia and glucose intolerance (GK > Wistar). Serum total cholesterol (GKs only), low-density lipoprotein (LDL) cholesterol (both strains), and free fatty acids (GK > Wistar) levels increased; however, no acrolein-induced changes were noted in branched-chain amino acid or insulin levels. These responses corresponded with a significant increase in corticosterone and modest but insignificant increases in adrenaline in both strains, suggesting activation of the HPA axis. Collectively, these data demonstrate that acrolein exposure has a profound effect on nasal and pulmonary inflammation, as well as glucose and lipid metabolis

OPTIMIZING THE PAKS METHOD FOR MEASURING AIRBORNE ACROLEIN

EPA Science Inventory

Airborne acrolein is produced from the combustion of fuel and tobacco and is of concern due to its potential for respiratory tract irritation and other adverse health effects. Active sampling with DNPH-coated solid sorbents has been widely used for sampling airborne carbonyls; ...

Acute and long-term ocular effects of acrolein vapor on the eyes and potential therapies.

PubMed

Dachir, Shlomit; Cohen, Maayan; Gutman, Hila; Cohen, Liat; Buch, Hillel; Kadar, Tamar

2015-01-01

Acrolein is a potent irritant and a vesicant that was used by the French during WWI as the warfare agent named: "papite". Nowadays, it is produced in large amounts all over the world in the industry for the production of acrylic acid and for agriculture use as herbicide. The aim of this study was to characterize the effects of acute eye exposure to acrolein vapor and to evaluate the efficacy of a topical post-exposure combination treatment with a local anesthetic and a steroid. Rabbit eyes were exposed to three doses of acrolein vapor (low, intermediate and high) and treated topically with either 0.4% benoxinate hydrochloride (localin, for 2 h) or dexamethasone (dexamycin, for 6 days) or a combination of both drugs. Clinical follow-up using slit lamp examinations and histological evaluation was performed 4 weeks post-exposure. Acrolein vapor caused immediate eye closure with excess tearing, corneal erosions and severe inflammation of the anterior chamber. This was followed by corneal neovascularization (NV) starting as early as 1 week post-exposure. The damage to the eyes was long lasting, and at 4 weeks following exposure, significant pathological changes were observed. Immediate post-exposure application of the local anesthetic, localin, prevented the eye closure, and the dexamycin treatment reduced significantly the initial inflammation as well as the extent and incidence of corneal NV. Short-term eye exposure to the irritant acrolein may result in immediate eye closure and long lasting pathologies that could lead to blindness. An anti-inflammatory treatment combined with short-term application of a local anesthetic prevents incapacitation and might minimize significantly the extent of eye injuries.

Selective Catalysis in Nanoparticle Metal-Organic Framework Composites

NASA Astrophysics Data System (ADS)

Stephenson, Casey Justin

The design of highly selective catalysts are becoming increasingly important, especially as chemical and pharmaceutical industries seek to improve atom economy and minimize energy intensive separations that are often required to separate side products from the desired product. Enzymes are among the most selective of all catalysts, generally operating through molecular recognition whereby an active site analogous to a lock and the substrate is analogous to a key. The assembly of a porous, crystalline material around a catalytically active metal particle could serve as an artificial enzyme. In this vein, we first synthesized the polyvinylpyrrolidone (PVP) coated nanoparticles of interest and then encapsulated them within zeolitic imidazolate framework 8 or ZIF-8. 2.8 nm Pt-PVP nanoparticles, which were encapsulated within ZIF-8 to form Pt ZIF-8 composite. Pt ZIF-8 was inactive for the hydrogenation of cyclic olefins such as cis-cyclooctene and cis-cyclohexene while the composite proved to be a highly selective catalyst for the hydrogenation of terminal olefins, hydrogenating trans-1,3-hexadiene to 3-hexene in 95% selectivity after 24 hours under 1 bar H2. We extended our encapsulation method to sub-2 nm Au nanoparticles to form Au ZIF-8. Au ZIF-8 served as a highly chemoselective catalyst for the hydrogenation of crotonaldehyde an alpha,beta-unsaturated aldehyde, to crotyl alcohol an alpha,beta-unsaturated alcohol, in 90-95% selectivity. In order to investigate nanoparticle size effects on selectivity, 6-10 nm Au nanoparticles were encapsulated within ZIF-8 to form Au6 ZIF-8. Control catalysts with nanoparticles supported on the surface of ZIF-8 were synthesized as well, Au/ZIF-8 and Au6/ZIF-8. Au6 ZIF-8 hydrogenated crotonaldehyde in 85% selectivity towards the unsaturated alcohol. Catalysts with nanoparticles supported on the exterior of ZIF-8 were far less selective towards the unsaturated alcohol. Post-catalysis transmission electron microscopy analysis of Au ZIF-8 and Au/ZIF-8 shows that the nanoparticles of Au ZIF-8 remain within experimental uncertainty and unchanged, whereas Au nanoparticles of Au/ZIF suffered from server sintering. We performed solvent assisted linker exchange, a single-crystal to single-crystal transformation, on Pt ZIF-8 to exchange the 2-methylimidazole linkers with imidazole to form Pt SALEM-2. Since Pt SALEM-2 should have larger apertures than Pt ZIF-8, we investigated Pt ZIF-8 and Pt SALEM-2 as catalysts for the hydrogenation of substrates with increasingly larger kinetic diameter: 1-octene, cis-cyclohexene, and beta-pinene. Both catalysts were active for the hydrogenation of 1-octene, while only Pt SALEM-2 was active for cis-cyclohexene hydrogenation. Neither catalyst was active for the hydrogenation of beta-pinene, indicating that the Pt nanoparticles remained well encapsulated throughout the SALE process.

High-resolution synchrotron infrared spectroscopy of acrolein: The vibrational levels between 700 and 820 cm-1

NASA Astrophysics Data System (ADS)

McKellar, A. R. W.; Billinghurst, B. E.

2015-09-01

The weak combination bands ν12 + ν18 and ν17 + ν18 of trans-acrolein in the 700-760 cm-1 region are observed at high resolution (<0.001 cm-1) using spectra obtained at the Canadian Light Source synchrotron radiation facility. A detailed rotational analysis of the 121181 and 171181 upper states is made which includes the nearby perturbing states 185, 132181, and 131183. Taking the results of this 5-state fit, together with earlier results on lower lying vibrations, we now have experimental characterization for all 15 excited vibrational states of acrolein lying below 820 cm-1.

Acrolein Causes TRPA1-Mediated Sensory Irritation and Indirect Potentiation of TRPV1-Mediated Pulmonary Chemoreflex Response

EPA Science Inventory

We previously demonstrated that acute exposure to acrolein causes immediate sensory irritation, with rapid decrease in heart rate (HR) and increase in inspiratory time (Ti), and potentiation of pulmonary chemoreflex response 24hrs later; of these effects only the latter is mediat...

Transient receptor potential cation channel A1 (TRPA1) mediates changes in heart rate variability following a single exposure to acrolein in mice

EPA Science Inventory

The data show that a single exposure to acrolein causes autonomic imbalance in mice through the TRPA1 sensor and subsequent cardiac dysfunction. Human and animal studies have shown that short-term air pollution exposure causes...

Simultaneous exposure to concentrated ambient particles and acrolein causes cardiac effects mediated by parasympathetic modulation in mice

EPA Science Inventory

This study shows that exposure to CAPs and acrolein causes an increase in HRV that is mediated by the parasympathetic nervous system. Numerous studies show that short-term air pollution exposure modulates heart rate variability (HRV), which is an indicator of autonomic influence...

Spermine oxidase promotes bile canalicular lumen formation through acrolein production.

PubMed

Uemura, Takeshi; Takasaka, Tomokazu; Igarashi, Kazuei; Ikegaya, Hiroshi

2017-11-01

Spermine oxidase (SMOX) catalyzes oxidation of spermine to generate spermidine, hydrogen peroxide (H 2 O 2 ) and 3-aminopropanal, which is spontaneously converted to acrolein. SMOX is induced by a variety of stimuli including bacterial infection, polyamine analogues and acetaldehyde exposure. However, the physiological functions of SMOX are not yet fully understood. We investigated the physiological role of SMOX in liver cells using human hepatocellular carcinoma cell line HepG2. SMOX localized to the bile canalicular lumen, as determined by F-actin staining. Knockdown of SMOX reduced the formation of bile canalicular lumen. We also found that phospho-Akt (phosphorylated protein kinase B) was localized to canalicular lumen. Treatment with Akt inhibitor significantly reduced the formation of bile canalicular lumen. Acrolein scavenger also inhibited the formation of bile canalicular lumen. PTEN, phosphatase and tensin homolog and an inhibitor of Akt, was alkylated in a SMOX-dependent manner. Our results suggest that SMOX plays a central role in the formation of bile canalicular lumen in liver cells by activating Akt pathway through acrolein production.

Acrolein Exposure Blocks Down-Regulation of Cytokines and IgE Antibody in a Mucosal Tolerance Model but does not Alter Phenotypic Markers of Allergic Lung Disease

EPA Science Inventory

Acrolein (ACR) is a highly reactive upper airway toxicant that humans are exposed in a variety of environmental situations. Here we examined the effect of ACR exposure on development of immune tolerance in mice. To induce tolerance, female BALB/C mice were intranasally inoculate...

Evaluation of N-acetylcysteine and methylprednisolone as therapies for oxygen and acrolein-induced lung damage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Critchley, J.A.J.H.; Beeley, J.M.; Clark, R.J.

1990-04-01

Reactive oxidizing species are implicated in the etiology of a range of inhalational pulmonary injuries. Consequently, various free radical scavengers have been tested as potential prophylactic agents. The sulfydryl compound, N-acetylcysteine (NAC) is the only such compound clinically available for use in realistic dosages, and it is well established as an effective antidote for the hepatic and renal toxicity of paracetamol. Another approach in pulmonary injury prophylaxis is methylprednisolone therapy. The authors evaluated NAC and methylprednisolone in two rats models of inhalation injury: 40-hr exposure to >97% oxygen at 1.1 bar and 15-min exposure to acrolein vapor (210 ppm). Themore » increases in lung wet/dry weight ratios, seen with both oxygen and acrolein toxicity were reduced with both treatments. However, with oxygen, NAC therapy was associated with considerably increased mortality and histological changes. Furthermore, IP NAC administration resulted in large volumes of ascitic fluid. With acrolein, IV, NAC had no significant effect on mortality or pulmonary histological damage. Methylprednisolone had no beneficial effects on either the mortality or histological damage observed in either toxicity model. They caution against the ad hoc use of NAC in the management of inhalational pulmonary injury.« less

Exposure to Nicotine and Selected Toxicants in Cigarette Smokers Who Switched to Electronic Cigarettes: A Longitudinal Within-Subjects Observational Study

PubMed Central

Gawron, Michal; Smith, Danielle M.; Peng, Margaret; Jacob, Peyton; Benowitz, Neal L.

2017-01-01

Introduction: Electronic cigarettes (e-cigarettes) are purported to deliver nicotine aerosol without any toxic combustion products present in tobacco smoke. In this longitudinal within-subjects observational study, we evaluated the effects of e-cigarettes on nicotine delivery and exposure to selected carcinogens and toxicants. Methods: We measured seven nicotine metabolites and 17 tobacco smoke exposure biomarkers in the urine samples of 20 smokers collected before and after switching to pen-style M201 e-cigarettes for 2 weeks. Biomarkers were metabolites of 13 major carcinogens and toxicants in cigarette smoke: one tobacco-specific nitrosamine (NNK), eight volatile organic compounds (1,3-butadiene, crotonaldehyde, acrolein, benzene, acrylamide, acrylonitrile, ethylene oxide, and propylene oxide), and four polycyclic aromatic hydrocarbons (naphthalene, fluorene, phenanthrene, and pyrene). Changes in urine biomarkers concentration were tested using repeated measures analysis of variance. Results: In total, 45% of participants reported complete abstinence from cigarette smoking at 2 weeks, while 55% reported continued smoking. Levels of total nicotine and some polycyclic aromatic hydrocarbon metabolites did not change after switching from tobacco to e-cigarettes. All other biomarkers significantly decreased after 1 week of using e-cigarettes (p < .05). After 1 week, the greatest percentage reductions in biomarkers levels were observed for metabolites of 1,3-butadiene, benzene, and acrylonitrile. Total NNAL, a metabolite of NNK, declined by 57% and 64% after 1 and 2 weeks, respectively, while 3-hydroxyfluorene levels declined by 46% at week 1, and 34% at week 2. Conclusions: After switching from tobacco to e-cigarettes, nicotine exposure remains unchanged, while exposure to selected carcinogens and toxicants is substantially reduced. Implications: To our knowledge, this is the first study that demonstrates that substituting tobacco cigarettes with an e-cigarette may reduce user exposure to numerous toxicants and carcinogens otherwise present in tobacco cigarettes. Data on reduced exposure to harmful constituents that are present in tobacco cigarettes and e-cigarettes can aid in evaluating e-cigarettes as a potential harm reduction device. PMID:27613896

Exposure to Nicotine and Selected Toxicants in Cigarette Smokers Who Switched to Electronic Cigarettes: A Longitudinal Within-Subjects Observational Study.

PubMed

Goniewicz, Maciej L; Gawron, Michal; Smith, Danielle M; Peng, Margaret; Jacob, Peyton; Benowitz, Neal L

2017-02-01

Electronic cigarettes (e-cigarettes) are purported to deliver nicotine aerosol without any toxic combustion products present in tobacco smoke. In this longitudinal within-subjects observational study, we evaluated the effects of e-cigarettes on nicotine delivery and exposure to selected carcinogens and toxicants. We measured seven nicotine metabolites and 17 tobacco smoke exposure biomarkers in the urine samples of 20 smokers collected before and after switching to pen-style M201 e-cigarettes for 2 weeks. Biomarkers were metabolites of 13 major carcinogens and toxicants in cigarette smoke: one tobacco-specific nitrosamine (NNK), eight volatile organic compounds (1,3-butadiene, crotonaldehyde, acrolein, benzene, acrylamide, acrylonitrile, ethylene oxide, and propylene oxide), and four polycyclic aromatic hydrocarbons (naphthalene, fluorene, phenanthrene, and pyrene). Changes in urine biomarkers concentration were tested using repeated measures analysis of variance. In total, 45% of participants reported complete abstinence from cigarette smoking at 2 weeks, while 55% reported continued smoking. Levels of total nicotine and some polycyclic aromatic hydrocarbon metabolites did not change after switching from tobacco to e-cigarettes. All other biomarkers significantly decreased after 1 week of using e-cigarettes (p < .05). After 1 week, the greatest percentage reductions in biomarkers levels were observed for metabolites of 1,3-butadiene, benzene, and acrylonitrile. Total NNAL, a metabolite of NNK, declined by 57% and 64% after 1 and 2 weeks, respectively, while 3-hydroxyfluorene levels declined by 46% at week 1, and 34% at week 2. After switching from tobacco to e-cigarettes, nicotine exposure remains unchanged, while exposure to selected carcinogens and toxicants is substantially reduced. To our knowledge, this is the first study that demonstrates that substituting tobacco cigarettes with an e-cigarette may reduce user exposure to numerous toxicants and carcinogens otherwise present in tobacco cigarettes. Data on reduced exposure to harmful constituents that are present in tobacco cigarettes and e-cigarettes can aid in evaluating e-cigarettes as a potential harm reduction device. © The Author 2016. Published by Oxford University Press on behalf of the Society for Research on Nicotine and Tobacco. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Acrolein Exposure in Hookah Smokers and Non-Smokers Exposed to Hookah Tobacco Secondhand Smoke: Implications for Regulating Hookah Tobacco Products.

PubMed

Kassem, Nada O F; Kassem, Noura O; Liles, Sandy; Zarth, Adam T; Jackson, Sheila R; Daffa, Reem M; Chatfield, Dale A; Carmella, Steven G; Hecht, Stephen S; Hovell, Melbourne F

2018-03-06

Acrolein is a highly ciliatoxic agent, a toxic respiratory irritant, a cardiotoxicant, and a possible carcinogen present in tobacco smoke including hookah tobacco. 105 hookah smokers and 103 non-smokers attended exclusively hookah smoking social events at either a hookah lounge or private home, and provided urine samples the morning of and the morning after the event. Samples were analyzed for 3-hydroxypropylmercapturic acid (3-HPMA), a metabolite of acrolein. Geometric mean (GM) urinary 3-HPMA levels in hookah smokers and non-smokers exposed to secondhand smoke (SHS) increased significantly, 1.41 times, 95% CI = 1.15 to 1.74 and 1.39 times, 95% CI = 1.16 to 1.67, respectively, following a hookah social event. The highest increase (1.68 times, 95% CI = 1.15 to 2.45; p = 0.007) in 3-HPMA post a hookah social event was among daily hookah smokers (GM, from 1991 pmol/mg to 3348 pmol/mg). Pre-to-post event change in urinary 3-HPMA was significantly positively correlated with pre-to-post event change in urinary cotinine among hookah smokers at either location of hookah event, (ρ = 0.359, p = 0.001), and among non-smokers in hookah lounges (ρ = 0.369, p = 0.012). Hookah tobacco smoke is a source of acrolein exposure. Findings support regulating hookah tobacco products including reducing humectants and sugar additives, which are precursors of acrolein under certain pyrolysis conditions. We suggest posting health warning signs for indoor smoking in hookah lounges, and encouraging voluntary bans of smoking hookah tobacco in private homes. Our study is the first to quantify the increase in acrolein exposure in hookah smokers and non-smokers exposed to exclusively hookah tobacco SHS at hookah social events in homes or hookah lounges. Our findings provide additional support for regulating hookah tobacco product content, protecting non-smokers' health by posting health warning signs for indoor smoking in hookah lounges, and encouraging home bans on hookah tobacco smoking to safeguard vulnerable residents.

Mesoporous silica nanoparticles for treating spinal cord injury

NASA Astrophysics Data System (ADS)

White-Schenk, Désirée.; Shi, Riyi; Leary, James F.

2013-02-01

An estimated 12,000 new cases of spinal cord injury (SCI) occur every year in the United States. A small oxidative molecule responsible for secondary injury, acrolein, is an important target in SCI. Acrolein attacks essential proteins and lipids, creating a feed-forward loop of oxidative stress in both the primary injury area and the surrounding areas. A small molecule used and FDA-approved for hypertension, hydralazine, has been found to "scavenge" acrolein after injury, but its delivery and short half-life, as well as its hypertension effects, hinder its application for SCI. Nanomedical systems broaden the range of therapeutic availability and efficacy over conventional medicine. They allow for targeted delivery of therapeutic molecules to tissues of interest, reducing side effects of untargeted therapies in unwanted areas. Nanoparticles made from silica form porous networks that can carry therapeutic molecules throughout the body. To attenuate the acrolein cascade and improve therapeutic availability, we have used a one-step, modified Stober method to synthesize two types of silica nanoparticles. Both particles are "stealth-coated" with poly(ethylene) glycol (PEG) (to minimize interactions with the immune system and to increase circulation time), which is also a therapeutic agent for SCI by facilitating membrane repair. One nanoparticle type contains an amine-terminal PEG (SiNP-mPEG-Am) and the other possesses a terminal hydrazide group (SiNP-mPEG-Hz). The former allows for exploration of hydralazine delivery, loading, and controlled release. The latter group has the ability to react with acrolein, allowing the nanoparticle to scavenge directly. The nanoparticles have been characterized and are being explored using neuronal PC-12 cells in vitro, demonstrating the potential of novel silica nanoparticles for use in attenuating secondary injury after SCI.

Direct sp(3)C-H acroleination of N-aryl-tetrahydroisoquinolines by merging photoredox catalysis with nucleophilic catalysis.

PubMed

Feng, Zhu-Jia; Xuan, Jun; Xia, Xu-Dong; Ding, Wei; Guo, Wei; Chen, Jia-Rong; Zou, You-Quan; Lu, Liang-Qiu; Xiao, Wen-Jing

2014-04-07

Sequence catalysis merging photoredox catalysis (PC) and nucleophilic catalysis (NC) has been realized for the direct sp(3) C-H acroleination of N-aryl-tetrahydroisoquinoline (THIQ). The reaction was performed under very mild conditions and afforded products in 50-91% yields. A catalytic asymmetric variant was proved to be successful with moderate enantioselectivities (up to 83 : 17 er).

Dehydration of glycerol over niobia-supported silicotungstic acid catalysts.

PubMed

Lee, Young Yi; Ok, Hye Jeong; Moon, Dong Ju; Kim, Jong Ho; Park, Nam Cook; Kim, Young Chul

2013-01-01

Liquid-phase dehydration of glycerol to acrolein over nanosized niobia-supported silicotungstic acid catalysts was performed to investigate the effect of the silicotungstic acid loading on the catalytic performance of the catalysts. The catalysts were prepared by following an impregnation method with different HSiW loadings in the range of 10-50 wt%. The prepared catalysts were characterized by N2 physisorption, XRD, FT-IR, TPD of ammonia, and TGA. Dehydration of glycerol was conducted in an autoclave reactor under the conditions of controlled reaction temperatures under corresponding pressure. Increasing HSiW loading rapidly increased the acidity of HSiW/Nb205 catalyst and rate of glycerol conversion, but acrolein selectivity decreased due to enhanced deactivation of the catalyst by carbon deposit. Consequently, it was confirmed that catalytic activity for the dehydration of glycerol to acrolein was dependant on the acidity of catalyst and can be controlled by HSiW loading.

TRPA1 mediates changes in heart rate variability and cardiac ...

EPA Pesticide Factsheets

Short-term exposure to ambient air pollution is linked with adverse cardiovascular effects. While previous research focused primarily on particulate matter-induced responses, gaseous air pollutants also contribute to cause short-term cardiovascular effects. Mechanisms underlying such effects have not been adequately described; however, the immediate nature of the response suggests involvement of irritant neural activation and downstream autonomic dysfunction. Thus, this study examines the role of TRPA1, an irritant sensory receptor found in the airways, in the cardiac response of mice to acrolein and ozone. Conscious unrestrained wild-type C57BL/6 (WT) and TRPA1 knockout (KO) mice implanted with radiotelemeters were exposed once to 3ppm acrolein, 0.3ppm ozone, or filtered air. Heart rate (HR) and electrocardiogram (ECG) were recorded continuously before, during and after exposure. Analysis of ECG morphology, incidence of arrhythmia and heart rate variability (HRV) were performed. Cardiac mechanical function was assessed using a Langendorff perfusion preparation 24h post-exposure. Acrolein exposure increased HRV independent of HR, as well as incidence of arrhythmia. Acrolein also increased left ventricular developed pressure in WT mice at 24h post-exposure. Ozone did not produce any changes in cardiac function. Neither gas produced ECG effects, changes in HRV, arrhythmogenesis, or mechanical function in KO mice. These data demonstrate that a single exposure to ac

A DFT Investigation of the Mechanism of Propene Ammoxidation over α-Bismuth Molybdate

DOE PAGES

Licht, Rachel B.; Bell, Alexis T.

2016-11-17

We investigated the mechanisms and energetics for the propene oxidation and ammoxidation occurring on the (010) surface of Bi 2 Mo 3 O 12 using density functional theory (DFT). An energetically feasible sequence of elementary steps for propene oxidation to acrolein, propene ammoxidation to acrylonitrile, and acrolein ammoxidation to acrylonitrile is proposed. Consistent with experimental findings, the rate-limiting step for both propene oxidation and ammoxidation is the initial hydrogen abstraction from the methyl group of propene, which is calculated to have an apparent activation energy of 27.3 kcal/mol. The allyl species produced in this reaction is stabilized as an allylmore » alkoxide, which can then undergo hydrogen abstraction to form acrolein or react with ammonia adsorbed on under-coordinated surface Bi 3+ cations to form allylamine. Dehydrogenation of allylamine is shown to produce acrylonitrile, whereas reaction with additional adsorbed ammonia leads to the formation of acetonitrile and hydrogen cyanide. The dehydrogenation of allyalkoxide species is found to have a significantly higher activation barrier than reaction with adsorbed ammonia, consistent with the observation that very little acrolein is produced when ammonia is present. Finally, we found that rapid reoxidation of the catalyst surface to release wate the driving force for all reactions involving the cleavage of C-H or N-H bonds, because practically all of these steps are endothermic. (Chemical Equation Presented).« less

Early life persistent vitamin D deficiency exacerbates ...

EPA Pesticide Factsheets

Epidemiological and animal data have conclusively linked adverse cardiovascular outcomes to air pollution exposure. As such, cardiovascular function is maintained by adequate levels of certain essential micronutrients like vitamin D. Unfortunately, vitamin D deficiency (VDD) has become highly prevalent in the United States, as well as in the world, even affecting otherwise healthy individuals. My initial studies showed that VDD alters cardiac function, increases cardiac arrhythmia and HRV (i.e. indirect measure of autonomic tone) in mice; this response is further exacerbated after smog exposure. VDD has been shown to alter the responsiveness of transient receptor potential A1 (TRPA1) channels, which we have previously shown to be involved in cardiopulmonary dysfunction to acrolein, which is a ubiquitous air pollutant and potent TRPA1 agonist. The effect of VDD on TRPA1-induced air pollution responses is not known and is the purpose of this study. 3-week old mice were placed on a VDD or normal diet (ND) for 19 weeks and then implanted with radiotelemeters for the measurement of heart rate, electrocardiogram and HRV. Mice were exposed to filtered air then acrolein for 3 hours each on separate days. During exposure, ventilatory function and ECG were simultaneously recorded. Acrolein increased parasympathetic tone in ND mice, but not VDD mice during exposure. However, acrolein caused cardiac arrhythmias only in VDD mice during exposure. Similar to previous studies,

46 CFR Table 151.05 to Subpart 151... - Summary of Minimum Requirements

Code of Federal Regulations, 2011 CFR

2011-10-01

...% or more Phenol, see Phenol Cresylate spent caustic Atmos. Amb. III 1 i i 2 i Integral Gravity Open... spent caustic Crotonaldehyde Atmos. Amb. II 1 i i 2 i i Integral Gravity PV Restr. II G-1 NR Vent F Yes.... II G-2 NR Vent N Yes .50-73 NA NA G Caustic potash solution Atmos. Amb.Elev. III 1 i 2 i Integral...

46 CFR Table 151.05 to Subpart 151... - Summary of Minimum Requirements

Code of Federal Regulations, 2014 CFR

2014-10-01

...% or more Phenol, see Phenol Cresylate spent caustic Atmos. Amb. III 1 i i 2 i Integral Gravity Open... spent caustic Crotonaldehyde Atmos. Amb. II 1 i i 2 i i Integral Gravity PV Restr. II G-1 NR Vent F Yes.... II G-2 NR Vent N Yes .50-73 NA NA G Caustic potash solution Atmos. Amb.Elev. III 1 i 2 i Integral...

46 CFR Table 151.05 to Subpart 151... - Summary of Minimum Requirements

Code of Federal Regulations, 2013 CFR

2013-10-01

...% or more Phenol, see Phenol Cresylate spent caustic Atmos. Amb. III 1 i i 2 i Integral Gravity Open... spent caustic Crotonaldehyde Atmos. Amb. II 1 i i 2 i i Integral Gravity PV Restr. II G-1 NR Vent F Yes.... II G-2 NR Vent N Yes .50-73 NA NA G Caustic potash solution Atmos. Amb.Elev. III 1 i 2 i Integral...

46 CFR Table 151.05 to Subpart 151... - Summary of Minimum Requirements

Code of Federal Regulations, 2012 CFR

2012-10-01

...% or more Phenol, see Phenol Cresylate spent caustic Atmos. Amb. III 1 i i 2 i Integral Gravity Open... spent caustic Crotonaldehyde Atmos. Amb. II 1 i i 2 i i Integral Gravity PV Restr. II G-1 NR Vent F Yes... G-2 NR Vent N Yes .50-73 NA NA G Caustic potash solution Atmos. Amb.Elev. III 1 i 2 i Integral...

Colour removal and carbonyl by-production in high dose ozonation for effluent polishing.

PubMed

Mezzanotte, V; Fornaroli, R; Canobbio, S; Zoia, L; Orlandi, M

2013-04-01

Experimental tests have been conducted to investigate the efficiency and the by-product generation of high dose ozonation (10-60 mg O3 L(-1)) for complete colour removal from a treated effluent with an important component of textile dyeing wastewater. The effluent is discharged into an effluent-dominated stream where no dilution takes place, and, thus, the quality requirement for the effluents is particularly strict. 30, 60 and 90 min contact times were adopted. Colour was measured as absorbance at 426, 558 and 660 nm wavelengths. pH was monitored throughout the experiments. The experimental work showed that at 50 mg L(-1) colour removal was complete and at 60 mg O3 L(-1) the final aldehyde concentration ranged between 0.72 and 1.02 mg L(-1). Glyoxal and methylglyoxal concentrations were directly related to colour removal, whereas formaldehyde, acetaldehyde, acetone and acrolein were not. Thus, the extent of colour removal can be used to predict the increase in glyoxal and methylglyoxal concentrations. As colour removal can be assessed by a simple absorbance measurement, in contrast to the analysis of specific carbonyl compounds, which is much longer and complex, the possibility of using colour removal as an indicator for predicting the toxic potential of ozone by-products for textile effluents is of great value. Copyright © 2013 Elsevier Ltd. All rights reserved.

A screening-level assessment of the health risks of chronic smoke exposure for wildland firefighters.

PubMed

Booze, Thomas F; Reinhardt, Timothy E; Quiring, Sharon J; Ottmar, Roger D

2004-05-01

A screening health risk assessment was performed to assess the upper-bound risks of cancer and noncancer adverse health effects among wildland firefighters performing wildfire suppression and prescribed burn management. Of the hundreds of chemicals in wildland fire smoke, we identified 15 substances of potential concern from the standpoints of concentration and toxicology; these included aldehydes, polycyclic aromatic hydrocarbons, carbon monoxide, benzene, and respirable particulate matter. Data defining daily exposures to smoke at prescribed burns and wildfires, potential days of exposure in a year, and career lengths were used to estimate average and reasonable maximum career inhalation exposures to these substances. Of the 15 substances in smoke that were evaluated, only benzene and formaldehyde posed a cancer risk greater than 1 per million, while only acrolein and respirable particulate matter exposures resulted in hazard indices greater than 1.0. The estimated upper-bound cancer risks ranged from 1.4 to 220 excess cancers per million, and noncancer hazard indices ranged from 9 to 360, depending on the exposure group. These values only indicate the likelihood of adverse health effects, not whether they will or will not occur. The risk assessment process narrows the field of substances that deserve further assessment, and the hazards identified by risk assessment generally agree with those identified as a concern in occupational exposure assessments.

Indoor Air Quality and Asthma

PubMed Central

Holm, Stewart

2017-01-01

Numerous contaminants in indoor air and their potential to cause or exacerbate asthma continue to be a subject of public health concern. Many agents are causally associated with or can exacerbate asthma, particularly in children. For formaldehyde, an established respiratory irritant based on numerous studies, the evidence for an association with asthma is still considered only limited or suggestive. However, there is no evidence that indicates increased sensitivity to sensory irritation to formaldehyde in people often regarded as susceptible such as asthmatics. Acrolein, but not formaldehyde, was significantly associated with asthma in a large cohort of children. This prompted an evaluation of this highly irritating chemical that had never previously been considered in the context of the indoor air/childhood asthma issue. Because acrolein is more potent than formaldehyde as a respiratory irritant and ubiquitous in indoor air, it is plausible that previous studies on potential risk factors and childhood asthma may be confounded by formaldehyde acting as an unrecognized proxy for acrolein. PMID:28250718

Urinary 3-hydroxypropyl mercapturic acid (3-HPMA) concentrations in dogs with acute spinal cord injury due to intervertebral disc herniation.

PubMed

Sangster, A M; Zheng, L; Bentley, R T; Shi, R; Packer, R A

2017-01-01

The aim of this study was to investigate urinary 3-hydroxypropyl mercapturic acid (3-HPMA), a metabolite of acrolein, as a novel biomarker in acute spinal cord injury (ASCI) due to intervertebral disc herniation in dogs. Urine from 10 client-owned dogs with ASCI collected at presentation and 10 control dogs was analyzed for 3-HPMA. The median urinary 3-HPMA concentration in ASCI dogs was significantly higher than in control dogs, but was not correlated with the severity of ASCI. The median urinary 3-HPMA concentration in intact dogs was higher than in neutered dogs. Higher urinary 3-HPMA concentrations in dogs after ASCI support a role for acrolein, a cytotoxic by-product of lipid peroxidation, in canine ASCI. Urinary 3-HPMA could be used as a biomarker in future clinical trials to measure the effect of therapeutic intervention of reducing acrolein after ASCI. Copyright © 2016. Published by Elsevier Ltd.

Development of methodologies for identification and quantification of hazardous air pollutants from turbine engine emissions.

PubMed

Anneken, David; Striebich, Richard; DeWitt, Matthew J; Klingshirn, Christopher; Corporan, Edwin

2015-03-01

Aircraft turbine engines are a significant source of particulate matter (PM) and gaseous emissions in the vicinity of airports and military installations. Hazardous air pollutants (HAPs) (e.g., formaldehyde, benzene, naphthalene and other compounds) associated with aircraft emissions are an environmental concern both in flight and at ground level. Therefore, effective sampling, identification, and accurate measurement of these trace species are important to assess their environmental impact. This effort evaluates two established ambient air sampling and analysis methods, U.S. Environmental Protection Agency (EPA) Method TO-11A and National Institute for Occupational Safety and Health (NIOSH) Method 1501, for potential use to quantify HAPs from aircraft turbine engines. The techniques were used to perform analysis of the exhaust from a T63 turboshaft engine, and were examined using certified gas standards transferred through the heated sampling systems used for engine exhaust gaseous emissions measurements. Test results show that the EPA Method TO-11A (for aldehydes) and NIOSH Method 1501 (for semivolatile hydrocarbons) were effective techniques for the sampling and analysis of most HAPs of interest. Both methods showed reasonable extraction efficiencies of HAP species from the sorbent tubes, with the exception of acrolein, styrene, and phenol, which were not well quantified. Formaldehyde measurements using dinitrophenylhydrazine (DNPH) tubes (EPA method TO-11A) were accurate for gas-phase standards, and compared favorably to measurements using gas-phase Fourier-transform infrared (FTIR) spectroscopy. In general, these two standard methodologies proved to be suitable techniques for field measurement of turbine engine HAPs within a reasonable (5-10 minutes) sampling period. Details of the tests, the analysis methods, calibration procedures, and results from the gas standards and T63 engine tested using a conventional JP-8 jet fuel are provided. HAPs from aviation-related sources are important because of their adverse health and environmental impacts in and around airports and flight lines. Simpler, more convenient techniques to measure the important HAPs, especially aldehydes and volatile organic HAPs, are needed to provide information about their occurrence and assist in the development of engines that emit fewer harmful emissions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Corley, Richard A.; Kabilan, Senthil; Kuprat, Andrew P.

Coupling computational fluid dynamics (CFD) with physiologically based pharmacokinetic (PBPK) models is useful for predicting site-specific dosimetry of airborne materials in the respiratory tract and elucidating the importance of species differences in anatomy, physiology, and breathing patterns. Historically, these models were limited to discrete regions of the respiratory system. CFD/PBPK models have now been developed for the rat, monkey, and human that encompass airways from the nose or mouth to the lung. A PBPK model previously developed to describe acrolein uptake in nasal tissues was adapted to the extended airway models as an example application. Model parameters for each anatomicmore » region were obtained from the literature, measured directly, or estimated from published data. Airflow and site-specific acrolein uptake patterns were determined under steadystate inhalation conditions to provide direct comparisons with prior data and nasalonly simulations. Results confirmed that regional uptake was dependent upon airflow rates and acrolein concentrations with nasal extraction efficiencies predicted to be greatest in the rat, followed by the monkey, then the human. For human oral-breathing simulations, acrolein uptake rates in oropharyngeal and laryngeal tissues were comparable to nasal tissues following nasal breathing under the same exposure conditions. For both breathing modes, higher uptake rates were predicted for lower tracheo-bronchial tissues of humans than either the rat or monkey. These extended airway models provide a unique foundation for comparing dosimetry across a significantly more extensive range of conducting airways in the rat, monkey, and human than prior CFD models.« less

Influence of environmental parameters on production of the acrolein precursor 3-hydroxypropionaldehyde by Lactobacillus reuteri DSMZ 20016 and its accumulation by wine lactobacilli.

PubMed

Bauer, Rolene; du Toit, Maret; Kossmann, Jens

2010-01-31

Lactic acid bacteria belonging to the genus Lactobacillus are known to convert glycerol into 3-hydroxypropionaldehyde (3-HPA) during anaerobic glycerol fermentation. Wine quality can be gravely compromised by the accumulation of 3-HPA, due to its spontaneous conversion to acrolein under wine making conditions. Acrolein is not only a dangerous substance for the living cell, but has been implicated in the development of unpleasant bitterness in beverages. This study evaluates the effect of individual environmental parameters on 3-HPA production by Lactobacillus reuteri DSMZ 20016, which only proved possible under conditions that allow accumulation well below the threshold concentration affecting cell viability. 3-HPA production was optimal at pH 6 and in the presence of 300 mM glycerol. Production increased with an increase in cell concentration up to an OD(600) of 50, whereas higher cell concentrations inhibited accumulation. Data presented in this study suggest that 3-HPA plays a role in regulating its own production through quorum sensing. Glycerol dehydratase possessing bacterial strains isolated from South African red wine, L. pentosus and L. brevis, tested positive for 3-HPA accumulation. 3-HPA is normally intracellularly reduced to 1,3-propanediol. This is the first study demonstrating the ability of wine lactobacilli to accumulate 3-HPA in the fermentation media. Recommendations are made on preventing the formation of acrolein and its precursor 3-HPA in wine. Copyright 2009 Elsevier B.V. All rights reserved.

Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

NASA Astrophysics Data System (ADS)

Murillo, Luis E.

Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are also discussed. Chemisorption, TPD, FTIR using a batch reactor for the self-hydrogenation of cyclohexene and CO adsorbed on the bimetallic surfaces were carried out to correlate surface science findings with experiments on supported bimetallic catalysts. To expand the studies on the effect of bimetallic structures on hydrogenation reactions, molecules with multiple functional groups such as alpha,beta-unsaturated aldehydes were also investigated. Studies of selective hydrogenation of a,ss-unsaturated aldehydes toward the desired unsaturated alcohols are of interest for the production of fine chemicals and pharmaceuticals. In these compounds, competitive hydrogenation of the C=C and C=O bonds occurs. TPD and HREELS experiments of acrolein (CH2=CH-CH=O) on Pt-based bimetallic surfaces are performed to investigate their effects on the hydrogenation activity of the C-O bond. The production of the desired unsaturated alcohol, allyl alcohol, has been observed for the first time on Pt-Ni-Pt(111) under UHV conditions. However, the propionaldehyde yield is five times higher than the allyl alcohol yield. Thus, a preferential isomerization reaction of allyl alcohol to propionaldehyde is very likely to occur on the Pt-Ni-Pt(111) surface as observed on the desorption studies of allyl alcohol on this surface. The hydrogenation of acrolein is also carried out under UHV conditions on other 3d-transition metal/Pt(111) surfaces such as Co/Pt(111), Fe/Pt(111), and Cu/Pt(111). So far, the highest activity and allyl alcohol yield are found on the Pt-Ni-Pt(111) surface with pre-adsorbed hydrogen.

Comparison of Urinary Biomarkers of Exposure in Humans Using Electronic Cigarettes, Combustible Cigarettes, and Smokeless Tobacco.

PubMed

Lorkiewicz, Pawel; Riggs, Daniel W; Keith, Rachel J; Conklin, Daniel J; Xie, Zhengzhi; Sutaria, Saurin; Lynch, Blake; Srivastava, Sanjay; Bhatnagar, Aruni

2018-06-02

Cigarette smoking is associated with an increase in cardiovascular disease risk, attributable in part to reactive volatile organic chemicals (VOCs). However, little is known about the extent of VOC exposure due to the use of other tobacco products. We recruited 48 healthy, tobacco users in four groups: cigarette, smokeless tobacco, occasional users of first generation e-cigarette and e-cigarette menthol and 12 healthy nontobacco users. After abstaining for 48 h, tobacco users used an assigned product. Urine was collected at baseline followed by five collections over a 3-h period to measure urinary metabolites of VOCs, nicotine, and tobacco alkaloids. Urinary levels of nicotine were ≃2-fold lower in occasional e-cigarette and smokeless tobacco users than in the cigarette smokers; cotinine and 3-hydroxycotinine levels were similar in all groups. Compared with nontobacco users, e-cigarette users had higher levels of urinary metabolites of xylene, cyanide, styrene, ethylbenzene, and benzene at baseline and elevated urinary levels of metabolites of xylene, N,N-dimethylformamide, and acrylonitrile after e-cigarette use. Metabolites of acrolein, crotonaldehyde, and 1,3-butadiene were significantly higher in smokers than in users of other products or nontobacco users. VOC metabolite levels in smokeless tobacco group were comparable to those found in nonusers with the exception of xylene metabolite-2-methylhippuric acid (2MHA), which was almost three fold higher than in nontobacco users. Smoking results in exposure to a range of VOCs at concentrations higher than those observed with other products, and first generation e-cigarette use is associated with elevated levels of N,N-dimethylformamide and xylene metabolites. This study shows that occasional users of first generation e-cigarettes have lower levels of nicotine exposure than the users of combustible cigarettes. Compared with combustible cigarettes, e-cigarettes, and smokeless tobacco products deliver lower levels of most VOCs, with the exception of xylene, N,N-dimethylformamide, and acrylonitrile, whose metabolite levels were higher in the urine of e-cigarette users than nontobacco users. Absence of anatabine in the urine of e-cigarette users suggests that measuring urinary levels of this alkaloid may be useful in distinguishing between users of e-cigarettes and combustible cigarettes. However, these results have to be validated in a larger cohortcomprised of users of e-cigarettes of multiple brands.

Glycerol Dehydration to Acrolein Catalyzed by ZSM‐5 Zeolite in Supercritical Carbon Dioxide Medium

PubMed Central

Zou, Bin; Ren, Shoujie

2016-01-01

Abstract Supercritical carbon dioxide (SC‐CO2) has been used for the first time as a reaction medium for the dehydration of glycerol to acrolein catalyzed by a solid acid. Unprecedented catalyst stability over 528 hours of time‐on‐stream was achieved and the rate of coke deposition on the zeolite catalyst was the lowest among extensive previous studies, showing potential for industrial application. Coking pathways in SC‐CO2 were also elucidated for future development. The results have potential implications for other dehydration reactions catalyzed by solid acids. PMID:27796088

Kiln emissions and potters' exposures.

PubMed

Hirtle, B; Teschke, K; van Netten, C; Brauer, M

1998-10-01

Some ten thousand British Columbia potters work in small private studios, cooperative facilities, educational institutions, or recreation centers. There has been considerable concern that this diffuse, largely unregulated activity may involve exposures to unacceptable levels of kiln emissions. Pottery kiln emissions were measured at 50 sites--10 from each of 5 categories: professional studios, recreation centers, elementary schools, secondary schools, and colleges. Area monitoring was done 76 cm from firing kilns and 1.6 m above the floor to assess breathing zone concentrations of nitrogen dioxide, carbon monoxide, sulfur dioxide, fluorides, aldehydes, aluminum, antimony, arsenic, barium, beryllium, boron, cadmium, chromium, cobalt, copper, gold, iron, lead, lithium, magnesium, manganese, mercury, nickel, selenium, silver, vanadium, and zinc. Personal exposures to the same metals were measured at 24 sites. Almost all measured values were well below permissible concentrations for British Columbia work sites and American Conference of Governmental Industrial Hygienists (ACGIH) threshold limit values (TLVs) with the following two exceptions. A single firing duration (495 minute) acrolein measurement adjacent to an electric kiln (0.109 ppm) exceeded these guidelines. One 15-minute sulfur dioxide measurement collected adjacent to a gas kiln (5.7 ppm) exceeded the ACGIH short-term exposure limit. The fact that concentrations in small, ventilated kiln rooms ranked among the highest measured gives rise to concern that unacceptable levels of contamination may exist where small kiln rooms remain unventilated. Custom designed exhaust hoods and industrial heating, ventilating, and air-conditioning systems were the most effective ventilation strategies. Passive diffusion and wall/window fans were least effective.

Acrylamide formation in food: a mechanistic perspective.

PubMed

Yaylayan, Varoujan A; Stadler, Richard H

2005-01-01

Earliest reports on the origin of acrylamide in food have confirmed asparagine as the main amino acid responsible for its formation. Available evidence suggests that sugars and other carbonyl compounds play a specific role in the decarboxylation process of asparagine, a necessary step in the generation of acrylamide. It has been proposed that Schiff base intermediate formed between asparagine and the sugar provides a low energy alternative to the decarboxylation from the intact Amadori product through generation and decomposition of oxazolidin-5-one intermediate, leading to the formation of a relatively stable azomethine ylide. Literature data indicate the propensity of such protonated ylides to undergo irreversible 1,2-prototropic shift and produce, in this case, decarboxylated Schiff bases which can easily rearrange into corresponding Amadori products. Decarboxylated Amadori products can either undergo the well known beta-elimination process initiated by the sugar moiety to produce 3-aminopropanamide and 1-deoxyglucosone or undergo 1,2-elimination initiated by the amino acid moiety to directly generate acrylamide. On the other hand, the Schiff intermediate can either hydrolyze and release 3-aminopropanamide or similarly undergo amino acid initiated 1,2-elimination to directly form acrylamide. Other thermolytic pathways to acrylamide--considered marginal at this stage--via the Strecker aldehyde, acrolein, and acrylic acid, are also addressed. Despite significant progress in the understanding of the mechanistic aspects of acrylamide formation, concrete evidence for the role of the different proposed intermediates in foods is still lacking.

Microbial Engineering for Aldehyde Synthesis

PubMed Central

Kunjapur, Aditya M.

2015-01-01

Aldehydes are a class of chemicals with many industrial uses. Several aldehydes are responsible for flavors and fragrances present in plants, but aldehydes are not known to accumulate in most natural microorganisms. In many cases, microbial production of aldehydes presents an attractive alternative to extraction from plants or chemical synthesis. During the past 2 decades, a variety of aldehyde biosynthetic enzymes have undergone detailed characterization. Although metabolic pathways that result in alcohol synthesis via aldehyde intermediates were long known, only recent investigations in model microbes such as Escherichia coli have succeeded in minimizing the rapid endogenous conversion of aldehydes into their corresponding alcohols. Such efforts have provided a foundation for microbial aldehyde synthesis and broader utilization of aldehydes as intermediates for other synthetically challenging biochemical classes. However, aldehyde toxicity imposes a practical limit on achievable aldehyde titers and remains an issue of academic and commercial interest. In this minireview, we summarize published efforts of microbial engineering for aldehyde synthesis, with an emphasis on de novo synthesis, engineered aldehyde accumulation in E. coli, and the challenge of aldehyde toxicity. PMID:25576610

Glycerol Dehydration to Acrolein Catalyzed by ZSM-5 Zeolite in Supercritical Carbon Dioxide Medium.

PubMed

Zou, Bin; Ren, Shoujie; Ye, X Philip

2016-12-08

Supercritical carbon dioxide (SC-CO 2 ) has been used for the first time as a reaction medium for the dehydration of glycerol to acrolein catalyzed by a solid acid. Unprecedented catalyst stability over 528 hours of time-on-stream was achieved and the rate of coke deposition on the zeolite catalyst was the lowest among extensive previous studies, showing potential for industrial application. Coking pathways in SC-CO 2 were also elucidated for future development. The results have potential implications for other dehydration reactions catalyzed by solid acids. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

A carnosine intervention study in overweight human volunteers: bioavailability and reactive carbonyl species sequestering effect

NASA Astrophysics Data System (ADS)

Regazzoni, Luca; de Courten, Barbora; Garzon, Davide; Altomare, Alessandra; Marinello, Cristina; Jakubova, Michaela; Vallova, Silvia; Krumpolec, Patrik; Carini, Marina; Ukropec, Jozef; Ukropcova, Barbara; Aldini, Giancarlo

2016-06-01

Carnosine is a natural dipeptide able to react with reactive carbonyl species, which have been recently associated with the onset and progression of several human diseases. Herein, we report an intervention study in overweight individuals. Carnosine (2 g/day) was orally administered for twelve weeks in order to evaluate its bioavailability and metabolic fate. Two carnosine adducts were detected in the urine samples of all subjects. Such adducts are generated from a reaction with acrolein, which is one of the most toxic and reactive compounds among reactive carbonyl species. However, neither carnosine nor adducts have been detected in plasma. Urinary excretion of adducts and carnosine showed a positive correlation although a high variability of individual response to carnosine supplementation was observed. Interestingly, treated subjects showed a significant decrease in the percentage of excreted adducts in reduced form, accompanied by a significant increase of the urinary excretion of both carnosine and carnosine-acrolein adducts. Altogether, data suggest that acrolein is entrapped in vivo by carnosine although the response to its supplementation is possibly influenced by individual diversities in terms of carnosine dietary intake, metabolism and basal production of reactive carbonyl species.

Curcumin analog 1, 5-bis (2-trifluoromethylphenyl)-1, 4-pentadien-3-one exhibits enhanced ability on Nrf2 activation and protection against acrolein-induced ARPE-19 cell toxicity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yuan; Zou, Xuan; Cao, Ke

2013-11-01

Curcumin, a phytochemical agent in the spice turmeric, has received increasing attention for its anticancer, anti-inflammatory and antioxidant properties. However, application of curcumin has been limited due to its insolubility in water and poor bioavailability both clinically and experimentally. In addition, the protective effects and mechanisms of curcumin in eye diseases have been poorly studied. In the present study, we synthesized a curcumin analog, 1, 5-bis (2-trifluoromethylphenyl)-1, 4-pentadien-3-one (C3), which displayed improved protective effect against acrolein-induced toxicity in a human retinal pigment epithelial cell line (ARPE-19). At 5 μM, curcumin completely protected against acrolein-induced cell oxidative damage and preserved GSHmore » levels and mitochondrial function. Surprisingly, C3 displayed a complete protective effect at 0.5 μM, which was much more efficient than curcumin. Both 0.5 μM C3 and 5 μM curcumin induced Nrf2 nuclear translocation and Nrf2 target genes transcription similarly. Experiments using Nrf2 siRNA showed that the protective effects of curcumin and C3 were eliminated by Nrf2 knockdown. Additionally, both curcumin and C3 activated the PI3/Akt pathway, however, Nrf2 activation was independent of this pathway, and therefore, we hypothesized that both curcumin and C3 activated phase II enzymes via directly disrupting the Nrf2/Keap1 complex and promoting Nrf2's nuclear translocation. Since acrolein challenge of ARPE-19 cells has been used as a model of smoking and age-related macular degeneration (AMD), we concluded that the curcumin analog, C3, may be a more promising drug candidate for its potential application for the prevention and treatment of eye diseases, such as AMD. - Highlights: • We examine toxicity effects of cigarette smoking component acrolein in retina cells. • We report a more efficient curcumin analog (C3) protecting cellular function. • Mitochondrial function and phase II enzyme activation are the major targets of C3. • C3 is ten-fold more potent than curcumin on activating Nrf2 nuclear translocation. • Nrf2 translocation and Phase II enzyme induction are independent of PI3K/Akt pathway.« less

Lowest triplet (n, π*) electronic state of acrolein: Determination of structural parameters by cavity ringdown spectroscopy and quantum-chemical methods

NASA Astrophysics Data System (ADS)

Hlavacek, Nikolaus C.; McAnally, Michael O.; Drucker, Stephen

2013-02-01

The cavity ringdown absorption spectrum of acrolein (propenal, CH2=CH—CH=O) was recorded near 412 nm, under bulk-gas conditions at room temperature and in a free-jet expansion. The measured spectral region includes the 0^0_0 band of the T1(n, π*) ← S0 system. We analyzed the 0^0_0 rotational contour by using the STROTA computer program [R. H. Judge et al., J. Chem. Phys. 103, 5343 (1995)], 10.1063/1.470569, which incorporates an asymmetric rotor Hamiltonian for simulating and fitting singlet-triplet spectra. We used the program to fit T1(n, π*) inertial constants to the room-temperature contour. The determined values (cm-1), with 2σ confidence intervals, are A = 1.662 ± 0.003, B = 0.1485 ± 0.0006, C = 0.1363 ± 0.0004. Linewidth analysis of the jet-cooled spectrum yielded a value of 14 ± 2 ps for the lifetime of isolated acrolein molecules in the T1(n, π*), v = 0 state. We discuss the observed lifetime in the context of previous computational work on acrolein photochemistry. The spectroscopically derived inertial constants for the T1(n, π*) state were used to benchmark a variety of computational methods. One focus was on complete active space methods, such as complete active space self-consistent field (CASSCF) and second-order perturbation theory with a CASSCF reference function (CASPT2), which are applicable to excited states. We also examined the equation-of-motion coupled-cluster and time-dependent density function theory excited-state methods, and finally unrestricted ground-state techniques, including unrestricted density functional theory and unrestricted coupled-cluster theory with single and double and perturbative triple excitations. For each of the above methods, we or others [O. S. Bokareva et al., Int. J. Quantum Chem. 108, 2719 (2008)], 10.1002/qua.21803 used a triple zeta-quality basis set to optimize the T1(n, π*) geometry of acrolein. We find that the multiconfigurational methods provide the best agreement with fitted inertial constants, while the economical unrestricted Perdew-Burke-Ernzerhof exchange-correlation hybrid functional (UPBE0) technique performs nearly as well.

Aldehydes with high and low toxicities inactivate cells by damaging distinct cellular targets.

PubMed

Xie, Ming-Zhang; Shoulkamy, Mahmoud I; Salem, Amir M H; Oba, Shunya; Goda, Mizuki; Nakano, Toshiaki; Ide, Hiroshi

2016-04-01

Aldehydes are genotoxic and cytotoxic molecules and have received considerable attention for their associations with the pathogenesis of various human diseases. In addition, exposure to anthropogenic aldehydes increases human health risks. The general mechanism of aldehyde toxicity involves adduct formation with biomolecules such as DNA and proteins. Although the genotoxic effects of aldehydes such as mutations and chromosomal aberrations are directly related to DNA damage, the role of DNA damage in the cytotoxic effects of aldehydes is poorly understood because concurrent protein damage by aldehydes has similar effects. In this study, we have analysed how saturated and α,β-unsaturated aldehydes exert cytotoxic effects through DNA and protein damage. Interestingly, DNA repair is essential for alleviating the cytotoxic effect of weakly toxic aldehydes such as saturated aldehydes but not highly toxic aldehydes such as long α,β-unsaturated aldehydes. Thus, highly toxic aldehydes inactivate cells exclusively by protein damage. Our data suggest that DNA interstrand crosslinks, but not DNA-protein crosslinks and DNA double-strand breaks, are the critical cytotoxic DNA damage induced by aldehydes. Further, we show that the depletion of intracellular glutathione and the oxidation of thioredoxin 1 partially account for the DNA damage-independent cytotoxicity of aldehydes. On the basis of these findings, we have proposed a mechanistic model of aldehyde cytotoxicity mediated by DNA and protein damage. Copyright © 2016 Elsevier B.V. All rights reserved.

21 CFR 182.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2014 CFR

2014-04-01

... aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde... aldehyde, caprinaldehyde, aldehyde C-10). Ethyl acetate. Ethyl butyrate. 3-Methyl-3-phenyl glycidic acid ethyl ester (ethyl-methyl-phenyl-glycidate, so-called strawberry aldehyde, C-16 aldehyde). Ethyl...

Production of a novel neuromelanin at the sevoflurane-water interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roberts, Ryan D.; Fibuch, Eugene E.; Elisabeth Heal, M.

2007-11-09

Postoperative cognitive dysfunction (POCD) occurs in the elderly following surgery that requires inhaled anesthetics. The molecular mechanism associated with this process is unknown. This study examined the possible role of serotonin, a neurotransmitter involved in cognition. We observed that sevoflurane, a common inhaled anesthetic, formed a separate phase in water similar to that of chloroform. Additionally, sevoflurane sequestered acrolein, which is a lipid peroxidation product associated with aging and is elevated in the elderly brain. The enhanced partitioning of acrolein increased the focal concentration and hence reactivity to serotonin which preferentially occurred at the sevoflurane-water interface. The resulting product exhibitedmore » unique properties similar to catecholamine-derived neuromelanin.« less

Molecular Mechanism of Acrylamide Neurotoxicity: Lessons Learned from Organic Chemistry

PubMed Central

Gavin, Terrence

2012-01-01

Background: Acrylamide (ACR) produces cumulative neurotoxicity in exposed humans and laboratory animals through a direct inhibitory effect on presynaptic function. Objectives: In this review, we delineate how knowledge of chemistry provided an unprecedented understanding of the ACR neurotoxic mechanism. We also show how application of the hard and soft, acids and bases (HSAB) theory led to the recognition that the α,β-unsaturated carbonyl structure of ACR is a soft electrophile that preferentially forms covalent bonds with soft nucleophiles. Methods: In vivo proteomic and in chemico studies demonstrated that ACR formed covalent adducts with highly nucleophilic cysteine thiolate groups located within active sites of presynaptic proteins. Additional research showed that resulting protein inactivation disrupted nerve terminal processes and impaired neurotransmission. Discussion: ACR is a type-2 alkene, a chemical class that includes structurally related electrophilic environmental pollutants (e.g., acrolein) and endogenous mediators of cellular oxidative stress (e.g., 4-hydroxy-2-nonenal). Members of this chemical family produce toxicity via a common molecular mechanism. Although individual environmental concentrations might not be toxicologically relevant, exposure to an ambient mixture of type-2 alkene pollutants could pose a significant risk to human health. Furthermore, environmentally derived type-2 alkenes might act synergistically with endogenously generated unsaturated aldehydes to amplify cellular damage and thereby accelerate human disease/injury processes that involve oxidative stress. Conclusions: These possibilities have substantial implications for environmental risk assessment and were realized through an understanding of ACR adduct chemistry. The approach delineated here can be broadly applied because many toxicants of different chemical classes are electrophiles that produce toxicity by interacting with cellular proteins. PMID:23060388

Monitoring of selected skin- and breath-borne volatile organic compounds emitted from the human body using gas chromatography ion mobility spectrometry (GC-IMS).

PubMed

Mochalski, Paweł; Wiesenhofer, Helmut; Allers, Maria; Zimmermann, Stefan; Güntner, Andreas T; Pineau, Nicolay J; Lederer, Wolfgang; Agapiou, Agapios; Mayhew, Christopher A; Ruzsanyi, Veronika

2018-02-15

Human smuggling and associated cross-border crimes have evolved as a major challenge for the European Union in recent years. Of particular concern is the increasing trend of smuggling migrants hidden inside shipping containers or trucks. Therefore, there is a growing demand for portable security devices for the non-intrusive and rapid monitoring of containers to detect people hiding inside. In this context, chemical analysis of volatiles organic compounds (VOCs) emitted from the human body is proposed as a locating tool. In the present study, an in-house made ion mobility spectrometer coupled with gas chromatography (GC-IMS) was used to monitor the volatile moieties released from the human body under conditions that mimic entrapment. A total of 17 omnipresent volatile compounds were identified and quantified from 35 ion mobility peaks corresponding to human presence. These are 7 aldehydes (acrolein, 2-methylpropanal, 3-methylbutanal, 2-ethacrolein, n-hexanal, n-heptanal, benzaldehyde), 3 ketones (acetone, 2-pentanone, 4-methyl-2-pentanone), 5 esters (ethyl formate, ethyl propionate, vinyl butyrate, butyl acetate, ethyl isovalerate), one alcohol (2-methyl-1-propanol) and one organic acid (acetic acid). The limits of detection (0.05-7.2 ppb) and relative standard deviations (0.6-11%) should be sufficient for detecting these markers of human presence in field conditions. This study shows that GC-IMS can be used as a portable field detector of hidden or entrapped people. Copyright © 2018 Elsevier B.V. All rights reserved.

Measurements of volatile organic compounds emitted from plants in the metropolitan area of São Paulo City , Brazil.

NASA Astrophysics Data System (ADS)

Carvalho, L.; Pisani, S.; Pool, C.; Vasconcellos, P.

2003-04-01

The presence of the biogenic hydrocarbons in an NO_x-containing atmosphere can enhance ozone generation and the impact of volatile organic compounds (VOCs) emitted from vegetation on atmospheric chemistry has been investigated. No study of VOC emission rates from plant species has been carried out in São Paulo City, Brazil, prior to this work. This study is part of a three-years project on biogenic volatile organic compounds emissions from species of plants found in the vegetation of the São Paulo metropolitan area. Typical plants (Alchornea sidifolia, Cupania oblongifolia, Cecropia pachystachia, Casearia sylvestris, Machaerium villosum, Croton floribundus, Myrcia rostrata, Solanum erianthum and Ficus insípida) were selected and identical species were studied in urban, sub-urban and forest regions. Biogenic hydrocarbons were determined placing branches of plants in enclosures and measuring the accumulation of emitted compounds in an all-Teflon chamber, the cuvette system. Measuring ambient VOC concentration adsorptive preconcentration, followed by GC-MS after thermal desorption of the sample, was employed to determine components heavier than C_5. Collection of carbonyl compounds on 2, 4-dinitrophenylhydrazine coated particles followed by HPLC-UV was used to analyze low molecular weight carbonyl compounds. Emissions rates of isoprene, a-pinene, camphene and limonene ranged from 0.01 to 2.16 μg C/h.g and emissions rates of aldehydes (C_1 - C_6), acrolein, methacrolein, 2-butanone and acetone ranged from 0.04 to 4.20 μg C/h.g. Ambient and chamber temperatures, relative humidity, light intensity, O_3 and NO_x were monitored during experiments.

Hazardous air pollutants and asthma.

PubMed

Leikauf, George D

2002-08-01

Asthma has a high prevalence in the United States, and persons with asthma may be at added risk from the adverse effects of hazardous air pollutants (HAPs). Complex mixtures (fine particulate matter and tobacco smoke) have been associated with respiratory symptoms and hospital admissions for asthma. The toxic ingredients of these mixtures are HAPs, but whether ambient HAP exposures can induce asthma remains unclear. Certain HAPs are occupational asthmagens, whereas others may act as adjuncts during sensitization. HAPs may exacerbate asthma because, once sensitized, individuals can respond to remarkably low concentrations, and irritants lower the bronchoconstrictive threshold to respiratory antigens. Adverse responses after ambient exposures to complex mixtures often occur at concentrations below those producing effects in controlled human exposures to a single compound. In addition, certain HAPs that have been associated with asthma in occupational settings may interact with criteria pollutants in ambient air to exacerbate asthma. Based on these observations and past experience with 188 HAPs, a list of 19 compounds that could have the highest impact on the induction or exacerbation of asthma was developed. Nine additional compounds were identified that might exacerbate asthma based on their irritancy, respirability, or ability to react with biological macromolecules. Although the ambient levels of these 28 compounds are largely unknown, estimated exposures from emissions inventories and limited air monitoring suggest that aldehydes (especially acrolein and formaldehyde) and metals (especially nickel and chromium compounds) may have possible health risk indices sufficient for additional attention. Recommendations for research are presented regarding exposure monitoring and evaluation of biologic mechanisms controlling how these substances induce and exacerbate asthma.

Cold-start and chemical characterization of emissions from mobile sources in Mexico.

PubMed

Schifter, I; Díaz, L; Rodríguez, R

2010-10-01

In this work tailpipe and evaporative emissions from a set of normal and high emitter vehicle models, year 2006-2008 (low mileage) certified when new to meet the Tier 1 emission standard, were characterized for criteria pollutants (carbon monoxide, nitrogen oxides and hydrocarbons), and a suite of unregulated emissions including aliphatic and aromatic aldehydes, monocyclic aromatic compounds, 1,3 butadiene, n-hexane and acrolein. Data were obtained under the three different driving conditions of the United States Federal Test Procedure, FTP-75 cycle. High emissions of both regulated and unregulated pollutants were observed in the cold-start phase of the driving cycle for low mileage Tier 1 normal and high emitters engines. Data were compared with results obtained for a set of MY > 1992-2005 that included vehicles with no catalytic converters, Tier 0 and MY 2000-5 Tier 1 emission standard with high mileage. The calculated average cold-start emissions for normal emitters in grams are 0.93, 8.21 and 1.06 for NMHC CO, and NOx, respectively for Tier 1 low mileage vehicles. The reductions in emissions for Tier 1 normal emitters are 76%, 56% and 56% for NMHC, CO and NOx, respectively, but 58%, 30% and 25% for the high emitters. Differences in emission can be ascribed to the mileage accumulation more than technological improvements. Cold-start emissions account in the USA roughly 10% of emissions from gasoline-powered vehicles. In Mexico the fractions are likely to be higher because one must account also for the contribution of Tier 0 and the running exhausts emissions of vehicles with no catalytic converters.

Hazardous air pollutants and asthma.

PubMed Central

Leikauf, George D

2002-01-01

Asthma has a high prevalence in the United States, and persons with asthma may be at added risk from the adverse effects of hazardous air pollutants (HAPs). Complex mixtures (fine particulate matter and tobacco smoke) have been associated with respiratory symptoms and hospital admissions for asthma. The toxic ingredients of these mixtures are HAPs, but whether ambient HAP exposures can induce asthma remains unclear. Certain HAPs are occupational asthmagens, whereas others may act as adjuncts during sensitization. HAPs may exacerbate asthma because, once sensitized, individuals can respond to remarkably low concentrations, and irritants lower the bronchoconstrictive threshold to respiratory antigens. Adverse responses after ambient exposures to complex mixtures often occur at concentrations below those producing effects in controlled human exposures to a single compound. In addition, certain HAPs that have been associated with asthma in occupational settings may interact with criteria pollutants in ambient air to exacerbate asthma. Based on these observations and past experience with 188 HAPs, a list of 19 compounds that could have the highest impact on the induction or exacerbation of asthma was developed. Nine additional compounds were identified that might exacerbate asthma based on their irritancy, respirability, or ability to react with biological macromolecules. Although the ambient levels of these 28 compounds are largely unknown, estimated exposures from emissions inventories and limited air monitoring suggest that aldehydes (especially acrolein and formaldehyde) and metals (especially nickel and chromium compounds) may have possible health risk indices sufficient for additional attention. Recommendations for research are presented regarding exposure monitoring and evaluation of biologic mechanisms controlling how these substances induce and exacerbate asthma. PMID:12194881

Cerebellar Expression of Copper Chaperone for Superoxide, Cytosolic Cu/Zn-Superoxide Dismutase, 4-Hydroxy-2-Nonenal, Acrolein and Heat Shock Protein 32 in Patients with Menkes Kinky Hair Disease: Immunohistochemical Study

PubMed Central

Yokoyama, Atsushi; Ohno, Kousaku; Hirano, Asao; Shintaku, Masayuki; Kato, Masako; Hayashi, Kazuhiko; Kato, Shinsuke

2014-01-01

Background To clarify the pathogenesis of cerebellar Purkinje cell death in patients with Menkes kinky hair disease (MD), a disorder of copper absorption, we investigated the morphological and functional abnormalities of residual Purkinje cells in MD patients and the mechanism of cell death. Methods Seven MD patients and 39 neurologically normal autopsy cases were studied. We performed histopathological and quantitative analyses of the Purkinje cells. In addition, we used immunohistochemistry to detect copper-dependent enzymes [cytosolic Cu/Zn-superoxide dismutase (SOD1) and copper chaperone for superoxide dismutase (CCS)], oxidative stress markers [4-hydroxy-2-nonenal (HNE) and acrolein] and heat shock protein 32 (hsp 32). Results The surviving MD Purkinje cells showed abnormal development, such as somatic sprouts and heterotopic location. Due to maldevelopment and degeneration, dendrites showed the cactus and weeping willow patterns. Axonal degeneration led to the formation of torpedoes. Quantitative analysis revealed loss of approximately 50% of the Purkinje cells in MD patients. Almost all of the normal Purkinje cells were positive for immunostaining by anti-CCS and anti-SOD1 antibodies, with staining of the cell bodies, dendrites and axons. Normal Purkinje cells were not stained by antibodies for HNE, acrolein or hsp 32. In MD patients, the majority of Purkinje cells were positive for CCS, but the positive rate for SOD1 was only about 23%. Approximately 56%, 42% and 40% of the Purkinje cells of MD patients were positive for HNE, acrolein and hsp 32, respectively. Conclusion In MD patients, about 50% of the Purkinje cells have been lost due to maldevelopment and degeneration. In the residual Purkinje cells, CCS expression seems to be nearly normal as a protective response to decreased SOD1 activity due to copper deficiency. Because oxidative stress is elevated secondary to decreased SOD1 activity, hsp 32 is induced as another protective mechanism. PMID:25067875

Cerebellar expression of copper chaperone for superoxide, cytosolic cu/zn-superoxide dismutase, 4-hydroxy-2-nonenal, acrolein and heat shock protein 32 in patients with menkes kinky hair disease: immunohistochemical study.

PubMed

Yokoyama, Atsushi; Ohno, Kousaku; Hirano, Asao; Shintaku, Masayuki; Kato, Masako; Hayashi, Kazuhiko; Kato, Shinsuke

2014-03-01

To clarify the pathogenesis of cerebellar Purkinje cell death in patients with Menkes kinky hair disease (MD), a disorder of copper absorption, we investigated the morphological and functional abnormalities of residual Purkinje cells in MD patients and the mechanism of cell death. Seven MD patients and 39 neurologically normal autopsy cases were studied. We performed histopathological and quantitative analyses of the Purkinje cells. In addition, we used immunohistochemistry to detect copper-dependent enzymes [cytosolic Cu/Zn-superoxide dismutase (SOD1) and copper chaperone for superoxide dismutase (CCS)], oxidative stress markers [4-hydroxy-2-nonenal (HNE) and acrolein] and heat shock protein 32 (hsp 32). The surviving MD Purkinje cells showed abnormal development, such as somatic sprouts and heterotopic location. Due to maldevelopment and degeneration, dendrites showed the cactus and weeping willow patterns. Axonal degeneration led to the formation of torpedoes. Quantitative analysis revealed loss of approximately 50% of the Purkinje cells in MD patients. Almost all of the normal Purkinje cells were positive for immunostaining by anti-CCS and anti-SOD1 antibodies, with staining of the cell bodies, dendrites and axons. Normal Purkinje cells were not stained by antibodies for HNE, acrolein or hsp 32. In MD patients, the majority of Purkinje cells were positive for CCS, but the positive rate for SOD1 was only about 23%. Approximately 56%, 42% and 40% of the Purkinje cells of MD patients were positive for HNE, acrolein and hsp 32, respectively. In MD patients, about 50% of the Purkinje cells have been lost due to maldevelopment and degeneration. In the residual Purkinje cells, CCS expression seems to be nearly normal as a protective response to decreased SOD1 activity due to copper deficiency. Because oxidative stress is elevated secondary to decreased SOD1 activity, hsp 32 is induced as another protective mechanism.

Coniferyl aldehyde 5-hydroxylation and methylation direct syringyl lignin biosynthesis in angiosperms

PubMed Central

Osakabe, Keishi; Tsao, Cheng Chung; Li, Laigeng; Popko, Jacqueline L.; Umezawa, Toshiaki; Carraway, Daniel T.; Smeltzer, Richard H.; Joshi, Chandrashekhar P.; Chiang, Vincent L.

1999-01-01

A central question in lignin biosynthesis is how guaiacyl intermediates are hydroxylated and methylated to the syringyl monolignol in angiosperms. To address this question, we cloned cDNAs encoding a cytochrome P450 monooxygenase (LsM88) and a caffeate O-methyltransferase (COMT) from sweetgum (Liquidambar styraciflua) xylem. Mass spectrometry-based functional analysis of LsM88 in yeast identified it as coniferyl aldehyde 5-hydroxylase (CAld5H). COMT expressed in Escherichia coli methylated 5-hydroxyconiferyl aldehyde to sinapyl aldehyde. Together, CAld5H and COMT converted coniferyl aldehyde to sinapyl aldehyde, suggesting a CAld5H/COMT-mediated pathway from guaiacyl to syringyl monolignol biosynthesis via coniferyl aldehyde that contrasts with the generally accepted route to sinapate via ferulate. Although the CAld5H/COMT enzyme system can mediate the biosynthesis of syringyl monolignol intermediates through either route, kcat/Km of CAld5H for coniferyl aldehyde was ≈140 times greater than that for ferulate. More significantly, when coniferyl aldehyde and ferulate were present together, coniferyl aldehyde was a noncompetitive inhibitor (Ki = 0.59 μM) of ferulate 5-hydroxylation, thereby eliminating the entire reaction sequence from ferulate to sinapate. In contrast, ferulate had no effect on coniferyl aldehyde 5-hydroxylation. 5-Hydroxylation also could not be detected for feruloyl-CoA or coniferyl alcohol. Therefore, in the presence of coniferyl aldehyde, ferulate 5-hydroxylation does not occur, and the syringyl monolignol can be synthesized only from coniferyl aldehyde. Endogenous coniferyl, 5-hydroxyconiferyl, and sinapyl aldehydes were detected, consistent with in vivo operation of the CAld5H/COMT pathway from coniferyl to sinapyl aldehydes via 5-hydroxyconiferyl aldehyde for syringyl monolignol biosynthesis. PMID:10430877

ALDEHYDE DEHYDROGENASES EXPRESSION DURING POSTNATAL DEVELOPMENT: LIVER VS. LUNG

EPA Science Inventory

Aldehydes are highly reactive molecules present in the environment, and can be produced during biotransformation of xenobiotics. Although the lung can be a major target for aldehyde toxicity, development of aldehyde dehydrogenases (ALDHs), which detoxify aldehydes, in lung has be...

Two-carbon homologation of aldehydes and ketones to α,β-unsaturated aldehydes.

PubMed

Petroski, Richard J; Vermillion, Karl; Cossé, Allard A

2011-06-17

Phosphonate reagents were developed for the two-carbon homologation of aldehydes or ketones to unbranched- or methyl-branched α,β-unsaturated aldehydes. The phosphonate reagents, diethyl methylformyl-2-phosphonate dimethylhydrazone and diethyl ethylformyl-2-phosphonate dimethylhydrazone, contained a protected aldehyde group instead of the usual ester group. A homologation cycle entailed condensation of the reagent with the starting aldehyde, followed by removal of the dimethylhydrazone protective group with a biphasic mixture of 1 M HCl and petroleum ether. This robust two-step process worked with a variety of aldehydes and ketones. Overall isolated yields of unsaturated aldehyde products ranged from 71% to 86% after the condensation and deprotection steps.

Contribution of aldehyde oxidizing enzymes on the metabolism of 3,4-dimethoxy-2-phenylethylamine to 3,4-dimethoxyphenylacetic acid by guinea pig liver slices.

PubMed

Panoutsopoulos, Georgios I

2006-01-01

3,4-Dimethoxy-2-phenylethylamine is catalyzed to its aldehyde derivative by monoamine oxidase B, but the subsequent oxidation into the corresponding acid has not yet been studied. Oxidation of aromatic aldehydes is catalyzed mainly by aldehyde dehydrogenase and aldehyde oxidase. The present study examines the metabolism of 3,4-dimethoxy-2-phenylethylamine in vitro and in freshly prepared and cryopreserved guinea pig liver slices and the relative contribution of different aldehyde-oxidizing enzymes was estimated by pharmacological means. 3,4-Dimethoxy-2- phenylethylamine was converted into the corresponding aldehyde when incubated with monoamine oxidase and further oxidized into the acid when incubated with both, monoamine oxidase and aldehyde oxidase. In freshly prepared and cryopreserved liver slices, 3,4-dimethoxyphenylacetic acid was the main metabolite of 3,4-dimethoxy-2- phenylethylamine. 3,4-Dimethoxyphenylacetic acid formation was inhibited by 85% from disulfiram (aldehyde dehydrogenase inhibitor) and by 75-80% from isovanillin (aldehyde oxidase inhibitor), whereas allopurinol (xanthine oxidase inhibitor) inhibited acid formation by only 25-30%. 3,4- Dimethoxy-2-phenylethylamine is oxidized mainly to its acid, via 3,4-dimethoxyphenylacetaldehyde, by aldehyde dehydrogenase and aldehyde oxidase with a lower contribution from xanthine oxidase.

DIFFERENTIATING THE TOXICITY OF CARCINOGENIC ALDEHYDES FROM NONCARCINOGENIC ALDEHYDES IN THE RAT NOSE USING CDNA ARRAYS

EPA Science Inventory

Differentiating the Toxicity of Carcinogenic Aldehydes from Noncarcinogenic Aldehydes in the Rat Nose Using cDNA Arrays.

Formaldehyde is a widely used aldehyde in many industrial settings, the tanning process, household products, and is a contaminant in cigarette smoke. H...

27 CFR 24.183 - Use of distillates containing aldehydes.

Code of Federal Regulations, 2013 CFR

2013-04-01

... containing aldehydes. 24.183 Section 24.183 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX... distillates containing aldehydes. Distillates containing aldehydes may be received on wine premises for use in... fermentation of wine made from a different kind of fruit. Distillates containing aldehydes which are received...

27 CFR 24.183 - Use of distillates containing aldehydes.

Code of Federal Regulations, 2012 CFR

2012-04-01

... containing aldehydes. 24.183 Section 24.183 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX... distillates containing aldehydes. Distillates containing aldehydes may be received on wine premises for use in... fermentation of wine made from a different kind of fruit. Distillates containing aldehydes which are received...

27 CFR 24.183 - Use of distillates containing aldehydes.

Code of Federal Regulations, 2014 CFR

2014-04-01

... containing aldehydes. 24.183 Section 24.183 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX... distillates containing aldehydes. Distillates containing aldehydes may be received on wine premises for use in... fermentation of wine made from a different kind of fruit. Distillates containing aldehydes which are received...

27 CFR 24.183 - Use of distillates containing aldehydes.

Code of Federal Regulations, 2011 CFR

2011-04-01

... containing aldehydes. 24.183 Section 24.183 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX... distillates containing aldehydes. Distillates containing aldehydes may be received on wine premises for use in... fermentation of wine made from a different kind of fruit. Distillates containing aldehydes which are received...

Catalytic Transformation of Aldehydes with Nickel Complexes through η(2) Coordination and Oxidative Cyclization.

PubMed

Hoshimoto, Yoichi; Ohashi, Masato; Ogoshi, Sensuke

2015-06-16

Chemists no longer doubt the importance of a methodology that could activate and utilize aldehydes in organic syntheses since many products prepared from them support our daily life. Tremendous effort has been devoted to the development of these methods using main-group elements and transition metals. Thus, many organic chemists have used an activator-(aldehyde oxygen) interaction, namely, η(1) coordination, whereby a Lewis or Brønsted acid activates an aldehyde. In the field of coordination chemistry, η(2) coordination of aldehydes to transition metals by coordination of a carbon-oxygen double bond has been well-studied; this activation mode, however, is rarely found in transition-metal catalysis. In view of the distinctive reactivity of an η(2)-aldehyde complex, unprecedented reactions via this intermediate are a distinct possibility. In this Account, we summarize our recent results dealing with nickel(0)-catalyzed transformations of aldehydes via η(2)-aldehyde nickel and oxanickelacycle intermediates. The combination of electron-rich nickel(0) and strong electron-donating N-heterocyclic carbene (NHC) ligands adequately form η(2)-aldehyde complexes in which the aldehyde is highly activated by back-bonding. With Ni(0)/NHC catalysts, processes involving intramolecular hydroacylation of alkenes and homo/cross-dimerization of aldehydes (the Tishchenko reaction) have been developed, and both proceed via the simultaneous η(2) coordination of aldehydes and other π components (alkenes or aldehydes). The results of the mechanistic studies are consistent with a reaction pathway that proceeds via an oxanickelacycle intermediate generated by the oxidative cyclization with a nickel(0) complex. In addition, we have used the η(2)-aldehyde nickel complex as an effective activator for an organosilane in order to generate a silicate reactant. These reactions show 100% atom efficiency, generate no wastes, and are conducted under mild conditions.

Alkylation of an active-site cysteinyl residue during substrate-dependent inactivation of Escherichia coli S-adenosylmethionine decarboxylase.

PubMed

Diaz, E; Anton, D L

1991-04-23

S-Adenosylmethionine decarboxylase from Escherichia coli is a member of a small class of enzymes that uses a pyruvoyl prosthetic group. The pyruvoyl group is proposed to form a Schiff base with the substrate and then act as an electron sink facilitating decarboxylation. We have previously shown that once every 6000-7000 turnovers the enzyme undergoes an inactivation that results in a transaminated pyruvoyl group and the formation of an acrolein-like species from the methionine moiety. The acrolein then covalently alkylates the enzyme [Anton, D. L., & Kutny, R. (1987) Biochemistry 26, 6444]. After reduction of the alkylated enzyme with NaBH4, a tryptic peptide with the sequence Ala-Asp-Ile-Glu-Val-Ser-Thr-[S-(3-hydroxypropyl)Cys]-Gly-Val-Ile-Ser-Pro - Leu-Lys was isolated. This corresponds to acrolein alkylation of a cysteine residue in the second tryptic peptide from the NH2 terminal of the alpha-subunit [Anton, D. L., & Kutny, R. (1987) J. Biol. Chem. 262, 2817-2822]. The modified residue derived is from Cys-140 of the proenzyme [Tabor, C. W., & Tabor, H. (1987) J. Biol. Chem. 262, 16037-16040] and lies in the only sequence conserved between rat liver and E. coli S-adenosylmethionine decarboxylase [Pajunen et al. (1988) J. Biol. Chem. 263, 17040-17049]. We suggest that the alkylated Cys residue could have a role in the catalytic mechanism.

10 CFR 26.161 - Cutoff levels for validity testing.

Code of Federal Regulations, 2012 CFR

2012-01-01

... aliquot; (5) The presence of glutaraldehyde is verified using either an aldehyde test (aldehyde present... glutaraldehyde is determined using the same aldehyde test (aldehyde present) or the characteristic immunoassay...

10 CFR 26.161 - Cutoff levels for validity testing.

Code of Federal Regulations, 2013 CFR

2013-01-01

... aliquot; (5) The presence of glutaraldehyde is verified using either an aldehyde test (aldehyde present... glutaraldehyde is determined using the same aldehyde test (aldehyde present) or the characteristic immunoassay...

10 CFR 26.161 - Cutoff levels for validity testing.

Code of Federal Regulations, 2014 CFR

2014-01-01

... aliquot; (5) The presence of glutaraldehyde is verified using either an aldehyde test (aldehyde present... glutaraldehyde is determined using the same aldehyde test (aldehyde present) or the characteristic immunoassay...

10 CFR 26.161 - Cutoff levels for validity testing.

Code of Federal Regulations, 2010 CFR

2010-01-01

... aliquot; (5) The presence of glutaraldehyde is verified using either an aldehyde test (aldehyde present... glutaraldehyde is determined using the same aldehyde test (aldehyde present) or the characteristic immunoassay...

10 CFR 26.161 - Cutoff levels for validity testing.

Code of Federal Regulations, 2011 CFR

2011-01-01

... aliquot; (5) The presence of glutaraldehyde is verified using either an aldehyde test (aldehyde present... glutaraldehyde is determined using the same aldehyde test (aldehyde present) or the characteristic immunoassay...

Development and analysis of air quality modeling simulations for hazardous air pollutants

NASA Astrophysics Data System (ADS)

Luecken, D. J.; Hutzell, W. T.; Gipson, G. L.

The concentrations of five hazardous air pollutants were simulated using the community multi-scale air quality (CMAQ) modeling system. Annual simulations were performed over the continental United States for the entire year of 2001 to support human exposure estimates. Results are shown for formaldehyde, acetaldehyde, benzene, 1,3-butadiene and acrolein. Photochemical production in the atmosphere is predicted to dominate ambient formaldehyde and acetaldehyde concentrations, and to account for a significant fraction of ambient acrolein concentrations. Spatial and temporal variations are large throughout the domain over the year. Predicted concentrations are compared with observations for formaldehyde, acetaldehyde, benzene and 1,3-butadiene. Although the modeling results indicate an overall slight tendency towards underprediction, they reproduce episodic and seasonal behavior of pollutant concentrations at many monitors with good skill.

Deodorants: an experimental provocation study with cinnamic aldehyde.

PubMed

Bruze, Magnus; Johansen, J D; Andersen, K E; Frosch, P; Lepoittevin, J-P; Rastogi, S; Wakelin, S; White, I; Menné, T

2003-02-01

Axillary dermatitis is common and overrepresented in individuals with contact allergy to fragrances. Many individuals suspect their deodorants to be the incriminating products. Our aim was to investigate the significance of cinnamic aldehyde in deodorants for the development of axillary dermatitis when used by individuals with and without contact allergy to cinnamic aldehyde. Patch tests with deodorants and ethanol solutions with cinnamic aldehyde, and repeated open application tests with roll-on deodorants without and with cinnamic aldehyde at different concentrations, were performed in 37 patients with dermatitis, 20 without and 17 with contact allergy to cinnamic aldehyde. A repeated open application test with positive findings was noted only in patients hypersensitive to cinnamic aldehyde (P <.001) and only in the axilla to which the deodorants containing cinnamic aldehyde had been applied (P <.001). Deodorants containing cinnamic aldehyde in the concentration range 0.01% to 0.32%, used twice daily on healthy skin, can elicit axillary dermatitis within a few weeks.

Characterization of the Aldehydes and Their Transformations Induced by UV Irradiation and Air Exposure of White Guanxi Honey Pummelo (Citrus Grandis (L.) Osbeck) Essential Oil.

PubMed

Li, Li Jun; Hong, Peng; Chen, Feng; Sun, Hao; Yang, Yuan Fan; Yu, Xiang; Huang, Gao Ling; Wu, Li Ming; Ni, Hui

2016-06-22

Aldehydes are key aroma contributors of citrus essential oils. White Guanxi honey pummelo essential oil (WPEO) was investigated in its aldehyde constituents and their transformations induced by UV irradiation and air exposure by GC-MS, GC-O, and sensory evaluation. Nine aldehydes, i.e., octanal, nonanal, citronellal, decanal, trans-citral, cis-citral, perilla aldehyde, dodecanal, and dodecenal, were detected in WPEO. After treatment, the content of citronellal increased, but the concentrations of other aldehydes decreased. The aliphatic aldehydes were transformed to organic acids. Citral was transformed to neric acid, geranic acid, and cyclocitral. Aldehyde transformation caused a remarkable decrease in the minty, herbaceous, and lemon notes of WPEO. In fresh WPEO, β-myrcene, d-limonene, octanal, decanal, cis-citral, trans-citral, and dodecenal had the highest odor dilution folds. After the treatment, the dilution folds of decanal, cis-citral, trans-citral, and dodecenal decreased dramatically. This result provides information for the production and storage of aldehyde-containing products.

First general methods toward aldehyde enolphosphates.

PubMed

Barthes, Nicolas; Grison, Claude

2012-02-01

We herein report two innovative methods toward aldehyde enolphosphates and the first saccharidic aldehyde enolphosphates. Aldehyde enolphosphate function is worthwhile to be considered as a good phosphoenolpyruvate analogue. Copyright © 2011 Elsevier Inc. All rights reserved.

Direct catalytic asymmetric alpha-amination of aldehydes.

PubMed

List, Benjamin

2002-05-22

The first direct catalytic asymmetric alpha-amination of aldehydes is described herein. alpha-Unbranched aldehydes react in this novel proline-catalyzed reaction with dialkyl azodicarboxylates to give alpha-amino aldehydes in excellent yields and enantioselectivities.

Aldehydes in hydrothermal solution - Standard partial molal thermodynamic properties and relative stabilities at high temperatures and pressures

NASA Technical Reports Server (NTRS)

Schulte, Mitchell D.; Shock, Everett L.

1993-01-01

Aldehydes are common in a variety of geologic environments and are derived from a number of sources, both natural and anthropogenic. Experimental data for aqueous aldehydes were taken from the literature and used, along with parameters for the revised Helgeson-Kirkham-Flowers (HKF) equations of state, to estimate standard partial molal thermodynamic data for aqueous straight-chain alkyl aldehydes at high temperatures and pressures. Examples of calculations involving aldehydes in geological environments are given, and the stability of aldehydes relative to carboxylic acids is evaluated. These calculations indicate that aldehydes may be intermediates in the formation of carboxylic acids from hydrocarbons in sedimentary basin brines and hydrothermal systems like they are in the atmosphere. The data and parameters summarized here allow evaluation of the role of aldehydes in the formation of prebiotic precursors, such as amino acids and hydroxy acids on the early Earth and in carbonaceous chondrite parent bodies.

'Real-world' compensatory behaviour with low nicotine concentration e-liquid: subjective effects and nicotine, acrolein and formaldehyde exposure.

PubMed

Dawkins, Lynne; Cox, Sharon; Goniewicz, Maciej; McRobbie, Hayden; Kimber, Catherine; Doig, Mira; Kośmider, Leon

2018-06-07

To compare the effects of i) high versus low nicotine concentration e-liquid, ii) fixed versus adjustable power and iii) the interaction between the two on: a) vaping behaviour, b) subjective effects, c) nicotine intake, and d) exposure to acrolein and formaldehyde in e-cigarette users vaping in their everyday setting. Counterbalanced, repeated measures with four conditions: i) low nicotine (6 mg/mL)/fixed power; ii) low nicotine/adjustable power; iii) high nicotine (18 mg/mL)/fixed power; iv) high nicotine/adjustable power. London and the South East, England. Twenty experienced e-cigarette users (recruited between September 2016 and February 2017) vaped ad libitum using an eVic Supreme™ with a 'Nautilus Aspire' tank over four weeks (one week per condition). Puffing patterns (daily puff number [PN], puff duration [PD], inter-puff interval [IPI]), mL of e-liquid consumed, changes to power (where permitted), and subjective effects (urge to vape, nicotine withdrawal symptoms) were measured in each condition. Nicotine intake was measured via salivary cotinine. 3-hydroxypropylmercapturic acid (3-HPMA), a metabolite of the toxicant acrolein, and formate, a metabolite of the carcinogen formaldehyde, were measured in urine. There was a significant nicotine concentration x power interaction for PD (p<0.01). PD was longer with low nicotine/fixed power compared with i) high nicotine/fixed power (p< 0.001 and ii) low nicotine/adjustable power (p< 0.01). PN and liquid consumed were higher in the low versus high nicotine condition (main effect of nicotine, p<0.05). Urge to vape and withdrawal symptoms were lower, and nicotine intake was higher, in the high nicotine condition (main effects of nicotine: p<0.01). Whilst acrolein levels did not differ, there was a significant nicotine x power interaction for formaldehyde (p<0.05). Use of a lower nicotine concentration e-liquid may be associated with compensatory behaviour (e.g., higher number and duration of puffs) and increases in negative affect, urge to vape, and formaldehyde exposure. This article is protected by copyright. All rights reserved.

Toward aldehyde and alkane production by removing aldehyde reductase activity in Escherichia coli.

PubMed

Rodriguez, Gabriel M; Atsumi, Shota

2014-09-01

Advances in synthetic biology and metabolic engineering have enabled the construction of novel biological routes to valuable chemicals using suitable microbial hosts. Aldehydes serve as chemical feedstocks in the synthesis of rubbers, plastics, and other larger molecules. Microbial production of alkanes is dependent on the formation of a fatty aldehyde intermediate which is converted to an alkane by an aldehyde deformylating oxygenase (ADO). However, microbial hosts such as Escherichia coli are plagued by many highly active endogenous aldehyde reductases (ALRs) that convert aldehydes to alcohols, which greatly complicates strain engineering for aldehyde and alkane production. It has been shown that the endogenous ALR activity outcompetes the ADO enzyme for fatty aldehyde substrate. The large degree of ALR redundancy coupled with an incomplete database of ALRs represents a significant obstacle in engineering E. coli for either aldehyde or alkane production. In this study, we identified 44 ALR candidates encoded in the E. coli genome using bioinformatics tools, and undertook a comprehensive screening by measuring the ability of these enzymes to produce isobutanol. From the pool of 44 candidates, we found five new ALRs using this screening method (YahK, DkgA, GldA, YbbO, and YghA). Combined deletions of all 13 known ALRs resulted in a 90-99% reduction in endogenous ALR activity for a wide range of aldehyde substrates (C2-C12). Elucidation of the ALRs found in E. coli could guide one in reducing competing alcohol formation during alkane or aldehyde production. Copyright © 2014 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

Facile synthesis of highly substituted 3-aminofurans from thiazolium salts, aldehydes, and dimethyl acetylenedicarboxylate.

PubMed

Ma, Cheng; Ding, Hanfeng; Wu, Guangming; Yang, Yewei

2005-10-28

[reaction: see text] A facile preparation of 3-aminofuran derivatives via multicomponent reactions of thiazole carbenes, aldehydes, and dimethyl acetylenedicarboxylate (DMAD) is reported. In this process, the thiazole carbenes, generated in situ from thiazolium salts, reacted with aldehydes and DMAD at -78 to 0 degree C in CH(2)Cl(2) to afford the substituted furans in moderate to good yields. Eight substituted thiazolium salts were employed as carbene precursors in the reaction. Besides aryl aldehydes, alpha,beta-unsaturated aldehydes, aliphatic aldehydes, and arenedial were also investigated and found to be applicable to this reaction.

Beyond benzoin condensation: trimerization of aldehydes via metal-free aerobic oxidative esterification of aldehydes with benzoin products in the presence of cyanide.

PubMed

Kim, Yoo-Jin; Kim, Na Yeun; Cheon, Cheol-Hong

2014-05-02

An unusual trimerization of aldehydes in the presence of cyanide via metal-free aerobic oxidative esterification under ambient conditions is described. Various aromatic aldehydes provided the corresponding oxidative esterification products in good to excellent yields. Mechanistic studies suggested that this reaction would proceed via a two-step sequence: cyanide-catalyzed benzoin condensation of aldehydes and subsequent aerobic oxidative esterification of aldehydes with the resultant benzoin products. The usefulness of this protocol was further demonstrated by converting the resulting trimeric products into other biologically important compounds.

Occupational exposure assessment of highway toll station workers to vehicle engine exhaust.

PubMed

Belloc-Santaliestra, Miriam; van der Haar, Rudolf; Molinero-Ruiz, Emilia

2015-01-01

Toll station workers are occupationally exposed to vehicle engine exhaust, a complex mixture of different chemical substances, including carcinogenic compounds. Therefore, a study was carried out on attendants of two highway toll stations to describe their occupational exposure to vehicle engine exhaust, based on a worst-case scenario approach. Personal sampling was conducted during the day shift for all attendants, testing for three groups of chemical substances: polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs) and aldehydes (formaldehyde and acrolein). Concentrations of total PAH, BTEX (benzene, toluene, ethylbenzene, and xylenes) and formaldehyde content varied between 97.60-336.08 ng/m3, 5.01-40.52 μg/m3, and 0.06-19.13 μg/m3, respectively. No clear relationships could be established between exposure levels and the number of vehicles. Furthermore, no differences were found between truck versus car lanes, or inside versus outside the tollbooth. Not all the detected VOCs were related to vehicle exhaust; some were consistent with the use of cleaning products. The measured concentrations were far below the established occupational exposure limits, but tended to be higher than values reported for outdoor urban environments. There are very few international studies assessing occupational exposures among toll station workers, and this is the first such study to be conducted in Spain. The results suggest that further, more detailed studies are necessary to characterize exposure properly, and ones which include other airborne pollutants, such as ultrafine particles. The comparison of the results to other similar studies was difficult, since no data related to some important exposure determinants have been provided. Therefore, it is recommended that these determinants be considered in future studies.

Consumption of deep-fried foods and risk of prostate cancer.

PubMed

Stott-Miller, Marni; Neuhouser, Marian L; Stanford, Janet L

2013-06-01

Evidence suggests that high-heat cooking methods may increase the risk of prostate cancer (PCa). The addition of oil/fat, as in deep-frying, may be of particular concern, and has not specifically been investigated in relation to PCa. Potential mechanisms include the formation of potentially carcinogenic agents such as aldehydes, acrolein, heterocyclic amines, polycyclic aromatic hydrocarbons, and acrylamide. We estimated odds ratios (OR) and 95% confidence intervals (CI) for the association between tertiles of intake of deep-fried foods from a food frequency questionnaire (French fries, fried chicken, fried fish, doughnuts and snack chips) and PCa risk, adjusted for potential confounders, among 1,549 cases and 1,492 controls. We additionally examined associations with more aggressive PCa (defined as regional/distant stage, elevated Gleason score or prostate-specific antigen level). Compared with <1/week, there was a positive association with PCa risk for intake ≥1/week of French fries (OR = 1.37; 95% CI, 1.11-1.69), fried chicken (OR = 1.30; 95% CI, 1.04-1.62), fried fish (OR = 1.32; 95% CI, 1.05-1.66), and doughnuts (OR = 1.35; 95% CI, 1.11-1.66). There was no association for snack chips (OR = 1.08; 95% CI, 0.89-1.32). Most of the estimates were slightly stronger for more aggressive disease (OR = 1.41; 95% CI, 1.04-1.92 for fried fish). Regular consumption of select deep-fried foods is associated with increased PCa risk. Whether this risk is specific to deep-fried foods, or whether it represents risk associated with regular intake of foods exposed to high heat and/or other aspects of the Western lifestyle, such as fast food consumption, remains to be determined. Copyright © 2013 Wiley Periodicals, Inc.

Consumption of deep-fried foods and risk of prostate cancera,b

PubMed Central

Stott-Miller, Marni; Neuhouser, Marian L.; Stanford, Janet L.

2013-01-01

Background Evidence suggests that high-heat cooking methods may increase the risk of prostate cancer (PCa). The addition of oil/fat, as in deep-frying, may be of particular concern, and has not specifically been investigated in relation to PCa. Potential mechanisms include the formation of potentially carcinogenic agents such as aldehydes, acrolein, heterocyclic amines, polycyclic aromatic hydrocarbons, and acrylamide. Methods We estimated odds ratios (OR) and 95% confidence intervals (CI) for the association between tertiles of intake of deep-fried foods from a food frequency questionnaire (French fries, fried chicken, fried fish, doughnuts and snack chips) and PCa risk, adjusted for potential confounders, among 1,549 cases and 1,492 controls. We additionally examined associations with more aggressive PCa (defined as regional/distant stage, elevated Gleason score or prostate specific antigen level). Results Compared with <1/week, there was a positive association with PCa risk for intake ≥ 1/week of French fries (OR=1.37; 95% CI, 1.11–1.69), fried chicken (OR=1.30; 95% CI, 1.04–1.62), fried fish (OR=1.32; 95% CI, 1.05–1.66), and doughnuts (OR=1.35; 95% CI, 1.11–1.66). There was no association for snack chips (OR=1.08; 95% CI, 0.89–1.32). Most of the estimates were slightly stronger for more aggressive disease (OR=1.41; 95% CI, 1.04–1.92 for fried fish). Conclusion Regular consumption of select deep-fried foods is associated with increased PCa risk. Whether this risk is specific to deep-fried foods, or whether it represents risk associated with regular intake of foods exposed to high heat and/or other aspects of the Western lifestyle, such as fast food consumption, remains to be determined. PMID:23335051

GR-891: a novel 5-fluorouracil acyclonucleoside prodrug for differentiation therapy in rhabdomyosarcoma cells

PubMed Central

Marchal, J A; Prados, J; Melguizo, C; Gómez, J A; Campos, J; Gallo, M A; Espinosa, A; Arena, N; Aránega, A

1999-01-01

Differentiation therapy provides an alternative treatment of cancer that overcomes the undesirable effects of classical chemotherapy, i.e. cytotoxicity and resistance to drugs. This new approach to cancer therapy focuses on the development of specific agents designed to selectively engage the process of terminal differentiation, leading to the elimination of tumorigenic cells and recovery of normal cell homeostasis. A series of new anti-cancer pyrimidine acyclonucleoside-like compounds were designed and synthesized by structural modifications of 5-fluorouracil, a drug which causes considerable cell toxicity and morbidity, and we evaluated their applicability for differentiation therapy in human rhabdomyosarcoma cells. We tested the pyrimidine derivative GR-891, (RS)-1-{[3-(2-hydroxyethoxy)-1-isopropoxy]propyl}-5-fluorouracil, an active drug which shows low toxicity in vivo and releases acrolein which is an aldehyde with anti-tumour activity. Both GR-891 and 5-fluorouracil caused time- and dose-dependent growth inhibition in vitro; however, GR-891 showed no cytotoxicity at low doses (22.5 μmol l−1 and 45 μmol l−1) and induced terminal myogenic differentiation in RD cells (a rhabdomyosarcoma cell line) treated for 6 days. Changes in morphological features and in protein organization indicated re-entry in the pathway of muscular maturation. Moreover, GR-891 increased adhesion capability mediated by the expression of fibronectin, and did not induce overexpression of P-glycoprotein, the mdr1 gene product, implicated in multidrug resistance. New acyclonucleoside-like compounds such as GR-891 have important potential advantages over 5-fluorouracil because of their lower toxicity and their ability to induce myogenic differentiation in rhabdomyosarcoma cells. Our results suggest that this drug may be useful for differentiation therapy in this type of tumour. 1999 Cancer Research Campaign PMID:10070873

Exposure to Cooking Fumes and Acute Reversible Decrement in Lung Functional Capacity.

PubMed

Neghab, Masoud; Delikhoon, Mahdieh; Norouzian Baghani, Abbas; Hassanzadeh, Jafar

2017-10-01

Being exposed to cooking fumes, kitchen workers are occupationally at risk of multiple respiratory hazards. No conclusive evidence exists as to whether occupational exposure to these fumes is associated with acute and chronic pulmonary effects and symptoms of respiratory diseases. To quantify the exposure levels and evaluate possible chronic and acute pulmonary effects associated with exposure to cooking fumes. In this cross-sectional study, 60 kitchen workers exposed to cooking fumes and 60 unexposed employees were investigated. The prevalence of respiratory symptoms among these groups was determined through completion of a standard questionnaire. Pulmonary function parameters were also measured before and after participants' work shift. Moreover, air samples were collected and analyzed to quantify their aldehyde, particle, and volatile organic contents. The mean airborne concentrations of formaldehyde, acetaldehyde, and acrolein was 0.45 (SD 0.41), 0.13 (0.1), and 1.56 (0.41) mg/m 3 , respectively. The mean atmospheric concentrations of PM 1 , PM 2.5 , PM 7 , PM 10 , and total volatile organic compounds (TVOCs) was 3.31 (2.6), 12.21 (5.9), 44.16 (16.6), 57 (21.55) μg/m 3 , and 1.31 (1.11) mg/m 3 , respectively. All respiratory symptoms were significantly (p<0.05) more prevalent in exposed group. No significant difference was noted between the pre-shift mean of spirometry parameters of exposed and unexposed group. However, exposed workers showed cross-shift decrease in most spirometry parameters, significantly lower than the pre-shift values and those of the comparison group. Exposure to cooking fumes is associated with a significant increase in the prevalence of respiratory symptoms as well as acute reversible decrease in lung functional capacity.

21 CFR 582.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2014 CFR

2014-04-01

... (benzoic aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde). Citral (2,6-dimethyloctadien-2,6-al-8, geranial, neral). Decanal (N-decylaldhehyde, capraldehyde, capric aldehyde, caprinaldehyde, aldehyde C-10). Diacetyl (2,3-butandeione). Ethyl acetate. Ethyl...

21 CFR 582.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2013 CFR

2013-04-01

... (benzoic aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde). Citral (2,6-dimethyloctadien-2,6-al-8, geranial, neral). Decanal (N-decylaldhehyde, capraldehyde, capric aldehyde, caprinaldehyde, aldehyde C-10). Diacetyl (2,3-butandeione). Ethyl acetate. Ethyl...

Two-carbon homologation of aldehydes and ketones to a,ß-unsaturated aldehydes

USDA-ARS?s Scientific Manuscript database

Phosphonate reagents were developed for the two-carbon homologation of aldehydes or ketones to unbranched- or methyl-branched a,ß-unsaturated aldehydes. The phosphonate reagents, diethyl methylformyl-2-phosphonate dimethylhydrazone and diethyl ethylformyl-2-phosphonate dimethylhydrazone, contained a...

21 CFR 582.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2012 CFR

2012-04-01

... (benzoic aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde). Citral (2,6-dimethyloctadien-2,6-al-8, geranial, neral). Decanal (N-decylaldhehyde, capraldehyde, capric aldehyde, caprinaldehyde, aldehyde C-10). Diacetyl (2,3-butandeione). Ethyl acetate. Ethyl...

21 CFR 582.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2010 CFR

2010-04-01

... (benzoic aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde). Citral (2,6-dimethyloctadien-2,6-al-8, geranial, neral). Decanal (N-decylaldhehyde, capraldehyde, capric aldehyde, caprinaldehyde, aldehyde C-10). Diacetyl (2,3-butandeione). Ethyl acetate. Ethyl...

21 CFR 582.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2011 CFR

2011-04-01

... (benzoic aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde). Citral (2,6-dimethyloctadien-2,6-al-8, geranial, neral). Decanal (N-decylaldhehyde, capraldehyde, capric aldehyde, caprinaldehyde, aldehyde C-10). Diacetyl (2,3-butandeione). Ethyl acetate. Ethyl...

Increased salivary aldehyde dehydrogenase 1 in non-reticular oral lichen planus.

PubMed

Mansourian, Arash; Shanbehzadeh, Najmeh; Kia, Seyed Javad; Moosavi, Mahdieh-Sadat

2017-01-01

Oral lichen planus is a potentially malignant disorder. One of the malignant transformation markers is cancer stem cells. One of the proposed marker for the detection of cancer stem cells's in head and neck cancer is aldehyde dehydrogenase. Recently it is shown that aldehyde dehydrogenase 1 expression in tissue samples is associated with oral lichen planus malignant transformation. This study evaluates salivary aldehyde dehydrogenase 1 in oral lichen planus. Thirty patients and 30 age and sex-matched healthy volunteers were recruited. Oral lichen planus was diagnosed based on the modified World Health Organization criteria. Subjects in the case group were divided into reticular and non-reticular forms. Unstimulated salivary samples were collected at 10-12 AM. Saliva concentrations of aldehyde dehydrogenase 1 were measured by ELISA. The differences between aldehyde dehydrogenase levels in the oral lichen planus group compared with the control group were not significant but aldehyde dehydrogenase in non-reticular oral lichen planus was significantly higher than that of the reticular form. This is a cross-sectional study, thus longitudinal studies in oral lichen planus may present similar or different results. The mechanism of malignant transformation in oral lichen planus is not defined. Previous analyses revealed that the aldehyde dehydrogenase 1 expression is significantly correlated with increased risk of transformation. This finding is consistent with our results because in the erosive and ulcerative forms of oral lichen planus, which have an increased risk of transformation, salivary aldehyde dehydrogenase 1 was overexpressed. A higher salivary aldehyde dehydrogenase level in non-reticular oral lichen planus can be a defensive mechanism against higher oxidative stress in these groups. Aldehyde dehydrogenase may be one of the malignant transformation markers in oral lichen planus. Further studies are needed for introducing aldehyde dehydrogenase as a prognostic indicator in certain lesions.

INHALATION EXPOSURE-RESPONSE ASSESSMENTS FOR FIVE CHEMICALS

EPA Science Inventory

Inhalation exposure-response assessments for five chemicals (acrolein, ethylene oxide, hexachlorocyclopentadiene, hydrogen sulfide, and phosgene) for less-than-lifetime durations are being developed to inform the development of the Inhalation Exposure-Response Analysis Methodolog...

Menthol attenuates respiratory irritation responses to multiple cigarette smoke irritants

PubMed Central

Willis, Daniel N.; Liu, Boyi; Ha, Michael A.; Jordt, Sven-Eric; Morris, John B.

2011-01-01

Menthol, the cooling agent in peppermint, is added to almost all commercially available cigarettes. Menthol stimulates olfactory sensations, and interacts with transient receptor potential melastatin 8 (TRPM8) ion channels in cold-sensitive sensory neurons, and transient receptor potential ankyrin 1 (TRPA1), an irritant-sensing channel. It is highly controversial whether menthol in cigarette smoke exerts pharmacological actions affecting smoking behavior. Using plethysmography, we investigated the effects of menthol on the respiratory sensory irritation response in mice elicited by smoke irritants (acrolein, acetic acid, and cyclohexanone). Menthol, at a concentration (16 ppm) lower than in smoke of mentholated cigarettes, immediately abolished the irritation response to acrolein, an agonist of TRPA1, as did eucalyptol (460 ppm), another TRPM8 agonist. Menthol's effects were reversed by a TRPM8 antagonist, AMTB. Menthol's effects were not specific to acrolein, as menthol also attenuated irritation responses to acetic acid, and cyclohexanone, an agonist of the capsaicin receptor, TRPV1. Menthol was efficiently absorbed in the respiratory tract, reaching local concentrations sufficient for activation of sensory TRP channels. These experiments demonstrate that menthol and eucalyptol, through activation of TRPM8, act as potent counterirritants against a broad spectrum of smoke constituents. Through suppression of respiratory irritation, menthol may facilitate smoke inhalation and promote nicotine addiction and smoking-related morbidities.— Willis, D. N., Liu, B., Ha, M. A., Jordt, S.-E., Morris, J. B. Menthol attenuates respiratory irritation responses to multiple cigarette smoke irritants. PMID:21903934

21 CFR 182.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2010 CFR

2010-04-01

... (parapropenyl anisole). Benzaldehyde (benzoic aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde). Citral (2,6-dimethyloctadien-2,6-al-8, gera-nial, neral). Decanal (N-decylaldehyde, capraldehyde, capric aldehyde, caprinaldehyde, aldehyde C-10). Ethyl acetate. Ethyl butyrate. 3...

21 CFR 182.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2011 CFR

2011-04-01

... (parapropenyl anisole). Benzaldehyde (benzoic aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde). Citral (2,6-dimethyloctadien-2,6-al-8, gera-nial, neral). Decanal (N-decylaldehyde, capraldehyde, capric aldehyde, caprinaldehyde, aldehyde C-10). Ethyl acetate. Ethyl butyrate. 3...

21 CFR 182.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2013 CFR

2013-04-01

... (parapropenyl anisole). Benzaldehyde (benzoic aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde). Citral (2,6-dimethyloctadien-2,6-al-8, gera-nial, neral). Decanal (N-decylaldehyde, capraldehyde, capric aldehyde, caprinaldehyde, aldehyde C-10). Ethyl acetate. Ethyl butyrate. 3...

21 CFR 182.60 - Synthetic flavoring substances and adjuvants.

Code of Federal Regulations, 2012 CFR

2012-04-01

... (parapropenyl anisole). Benzaldehyde (benzoic aldehyde). N-Butyric acid (butanoic acid). d- or l-Carvone (carvol). Cinnamaldehyde (cinnamic aldehyde). Citral (2,6-dimethyloctadien-2,6-al-8, gera-nial, neral). Decanal (N-decylaldehyde, capraldehyde, capric aldehyde, caprinaldehyde, aldehyde C-10). Ethyl acetate. Ethyl butyrate. 3...

DEVELOPMENTAL EXPRESSION OF ALDEHYDE DEHYDROGENASE IN RAT: A COMPARISON OF LIVER AND LUNG DEVELOPMENT

EPA Science Inventory

Metabolism is one of the major determinants for age-related susceptibility changes to chemicals. Aldehydes are highly reactive molecules present in the environment and can be produced during biotransformation of xenobiotics. Aldehyde dehydrogenases (ALDH) are important in aldehyd...

A Search for CD36 Ligands from Flavor Volatiles in Foods with an Aldehyde Moiety: Identification of Saturated Aliphatic Aldehydes with 9-16 Carbon Atoms as Potential Ligands of the Receptor.

PubMed

Tsuzuki, Satoshi; Amitsuka, Takahiko; Okahashi, Tatsuya; Kimoto, Yusaku; Inoue, Kazuo

2017-08-09

Volatile compounds with an aldehyde moiety such as (Z)-9-octadecenal are potential ligands for cluster of differentiation 36 (CD36), a transmembrane receptor that has recently been shown to play a role in mammalian olfaction. In this study, by performing an assay using a peptide mimic of human CD36, we aimed to discover additional ligands for the receptor from volatiles containing a single aldehyde group commonly found in human foods. Straight-chain, saturated aliphatic aldehydes with 9-16 carbons exhibited CD36 ligand activities, albeit to varying degrees. Notably, the activities of tridecanal and tetradecanal were higher than that of oleic acid, the most potent ligand among the fatty acids tested. Among the aldehydes other than aliphatic aldehydes, only phenylacetaldehyde showed a weak activity. These findings make a contribution to our knowledge of recognition mechanisms for flavor volatiles in foods with an aldehyde group.

Determination of linear aliphatic aldehydes in heavy metal containing waters by high-performance liquid chromatography using 2,4-dinitrophenylhydrazine derivatization.

PubMed

Lin, Yi-Liang; Wang, Po-Yen; Hsieh, Ling-Ling; Ku, Kuan-Hsuan; Yeh, Yun-Tai; Wu, Chien-Hou

2009-09-04

A simple and sensitive method is described for the determination of picomolar amounts of C(1)-C(9) linear aliphatic aldehydes in waters containing heavy metal ions. In this method, aldehydes were first derivatized with 2,4-dinitrophenylhydrazine (DNPH) at optimized pH 1.8 for 30 min and analyzed by HPLC with UV detector at 365 nm. Factors affecting the derivatization reaction of aldehydes and DNPH were investigated. Cupric ion, an example of heavy metals, is a common oxidative reagent, which may oxidize DNPH and greatly interfere with the determination of aldehydes. EDTA was used to effectively mask the interferences by heavy metal ions. The method detection limits for direct injection of derivatized most aldehydes except formaldehyde were of the order of 7-28 nM. The detection limit can be further lowered by using off-line C(18) adsorption cartridge enrichment. The recoveries of C(1)-C(9) aldehydes were 93-115% with a relative standard deviation of 3.6-8.1% at the 0.1 microM level for aldehydes. The HPLC-DNPH method has been applied for determining aldehyde photoproducts from Cu(II)-amino acid complex systems.

Substrate-Controlled Diastereoselectivity Reversal in NHC-Catalyzed Cross-Benzoin Reactions Using N-Boc-N-Bn-Protected α-Amino Aldehydes.

PubMed

Haghshenas, Pouyan; Quail, J Wilson; Gravel, Michel

2016-12-16

The effectiveness of utilizing N-Bn-N-Boc-α-amino aldehydes in cross-benzoin reactions with heteroaromatic aldehydes is demonstrated. The reaction is both chemoselective and syn-selective, making it complementary to the anti-selective cross-benzoin reaction of NHBoc-α-amino aldehydes. Good diastereoselectivity is obtained for a variety of amino aldehydes, including nonhindered ones. A Felkin-Anh model can be used to rationalize the observed diastereoselectivity.

40 CFR 721.5762 - Aromatic aldehyde phenolic resin (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aromatic aldehyde phenolic resin... Specific Chemical Substances § 721.5762 Aromatic aldehyde phenolic resin (generic). (a) Chemical substance... aromatic aldehyde phenolic resin (PMN P-01-573) is subject to reporting under this section for the...

40 CFR 721.639 - Amine aldehyde condensate.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Amine aldehyde condensate. 721.639... Substances § 721.639 Amine aldehyde condensate. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an amine aldehyde condensate (PMN P-94-1810...

40 CFR 721.5762 - Aromatic aldehyde phenolic resin (generic).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Aromatic aldehyde phenolic resin... Specific Chemical Substances § 721.5762 Aromatic aldehyde phenolic resin (generic). (a) Chemical substance... aromatic aldehyde phenolic resin (PMN P-01-573) is subject to reporting under this section for the...

40 CFR 721.639 - Amine aldehyde condensate.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Amine aldehyde condensate. 721.639... Substances § 721.639 Amine aldehyde condensate. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an amine aldehyde condensate (PMN P-94-1810...

New preparation of diethyl methylformylphosphonate dimethylhydrazone: A reagent for aldehyde homologation

USDA-ARS?s Scientific Manuscript database

The phosphonate reagent, diethyl methylformyl-2-phosphonate dimethylhydrazone contains a protected aldehyde group instead of the usual ester group. It can be used for the two-carbon homologation of aldehydes to a, ß-unsaturated aldehydes. The reagent can be prepared in good overall yield (82%) and...

40 CFR 721.639 - Amine aldehyde condensate.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Amine aldehyde condensate. 721.639... Substances § 721.639 Amine aldehyde condensate. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an amine aldehyde condensate (PMN P-94-1810...

40 CFR 721.639 - Amine aldehyde condensate.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Amine aldehyde condensate. 721.639... Substances § 721.639 Amine aldehyde condensate. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an amine aldehyde condensate (PMN P-94-1810...

40 CFR 721.5762 - Aromatic aldehyde phenolic resin (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Aromatic aldehyde phenolic resin... Specific Chemical Substances § 721.5762 Aromatic aldehyde phenolic resin (generic). (a) Chemical substance... aromatic aldehyde phenolic resin (PMN P-01-573) is subject to reporting under this section for the...

40 CFR 721.5762 - Aromatic aldehyde phenolic resin (generic).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Aromatic aldehyde phenolic resin... Specific Chemical Substances § 721.5762 Aromatic aldehyde phenolic resin (generic). (a) Chemical substance... aromatic aldehyde phenolic resin (PMN P-01-573) is subject to reporting under this section for the...

40 CFR 721.639 - Amine aldehyde condensate.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Amine aldehyde condensate. 721.639... Substances § 721.639 Amine aldehyde condensate. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an amine aldehyde condensate (PMN P-94-1810...

40 CFR 721.5762 - Aromatic aldehyde phenolic resin (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aromatic aldehyde phenolic resin... Specific Chemical Substances § 721.5762 Aromatic aldehyde phenolic resin (generic). (a) Chemical substance... aromatic aldehyde phenolic resin (PMN P-01-573) is subject to reporting under this section for the...

ELASTIN: DIMINISHED REACTIVITY WITH ALDEHYDE REAGENTS IN COPPER DEFICIENCY AND LATHYRISM

PubMed Central

Miller, E. J.; Fullmer, Harold M.

1966-01-01

Elastin fibers in the aortas of control, lathyritic, copper-supplemented, and copper-deficient chicks were examined histochemically and chemically for aldehyde content. Diminished staining for aldehydes was obtained in the fibers from the aortas of lathyritic and copper-deficient chicks. Chemical studies of elastin isolated from the aortas of control and lathyritic chicks showed an apparent loss of lysine residues in control elastin to be associated with an increase in aldehyde content providing evidence that lysine is converted to an aldehyde-containing intermediate during biosynthesis of desmosine and isodesmosine. Approximately 6 aldehyde groups were present for every 1000 amino acids in elastin isolated from the aortas of control animals, while the corresponding number in lathyritic elastin was 4. At least two types of aldehydes, saturated and α,β-unsaturated, appear to be associated with elastin, suggesting the presence of more than one intermediate between lysine and the desmosines. PMID:5941783

MASS SPECTROMETRY OF FATTY ALDEHYDES

PubMed Central

Berdyshev, Evgeny V.

2011-01-01

Fatty aldehydes are important components of the cellular lipidome. Significant interest has been developed towards the analysis of the short chain α,β-unsaturated and hydroxylated aldehydes formed as a result of oxidation of polyunsaturated fatty acids. Multiple gas chromatography-mass spectrometry (GC/MS) and subsequently liquid chromatography-mass spectrometry (LC/MS) approaches have been developed to identify and quantify short-chain as well as long-chain fatty aldehydes. Due to the ability to non-enzymaticaly form Schiff bases with amino groups of proteins, lipids, and with DNA guanidine, free aldehydes are viewed as a marker or metric of fatty acid oxidation and not the part of intracellular signaling pathways which has significantly limited the overall attention this group of molecules have received. This review provides an overview of current GC/MS and LC/MS approaches of fatty aldehyde analysis as well as discusses technical challenges standing in the way of free fatty aldehyde quantitation. PMID:21930240

Metabolism of 2-phenylethylamine and phenylacetaldehyde by precision-cut guinea pig fresh liver slices.

PubMed

Panoutsopoulos, Georgios I; Kouretas, Demetrios; Gounaris, Elias G; Beedham, Christine

2004-01-01

2-Phenylethylamine is an endogenous constituent of human brain and is implicated in cerebral transmission. It is also found in certain foodstuffs and may cause toxic side-effects in susceptible individuals. Metabolism of 2-phenylethylamine to phenylacetaldehyde is catalyzed by monoamine oxidase and the oxidation of the reactive aldehyde to its acid derivative is catalyzed mainly by aldehyde dehydrogenase and perhaps aldehyde oxidase, with xanthine oxidase having minimal transformation. The present investigation examines the metabolism of 2-phenylethylamine to phenylacetaldehyde in liver slices and compares the relative contribution of aldehyde oxidase, xanthine oxidase and aldehyde dehydrogenase activity in the oxidation of phenylacetaldehyde with precision-cut fresh liver slices in the presence/absence of specific inhibitors of each enzyme. In liver slices, phenylacetaldehyde was rapidly converted to phenylacetic acid. Phenylacetic acid was the main metabolite of 2-phenylethylamine, via the intermediate phenylacetaldehyde. Phenylacetic acid formation was completely inhibited by disulfiram (specific inhibitor of aldehyde dehydrogenase), whereas isovanillin (specific inhibitor of aldehyde oxidase) inhibited acid formation to a lesser extent and allopurinol (specific inhibitor of xanthine oxidase) had little or no effect. Therefore, in liver slices, phenylacetaldehyde is rapidly oxidized by aldehyde dehydrogenase and aldehyde oxidase with little or no contribution from xanthine oxidase.

Effects of cooking method, cooking oil, and food type on aldehyde emissions in cooking oil fumes.

PubMed

Peng, Chiung-Yu; Lan, Cheng-Hang; Lin, Pei-Chen; Kuo, Yi-Chun

2017-02-15

Cooking oil fumes (COFs) contain a mixture of chemicals. Of all chemicals, aldehydes draw a great attention since several of them are considered carcinogenic and formation of long-chain aldehydes is related to fatty acids in cooking oils. The objectives of this research were to compare aldehyde compositions and concentrations in COFs produced by different cooking oils, cooking methods, and food types and to suggest better cooking practices. This study compared aldehydes in COFs produced using four cooking oils (palm oil, rapeseed oil, sunflower oil, and soybean oil), three cooking methods (stir frying, pan frying, and deep frying), and two foods (potato and pork loin) in a typical kitchen. Results showed the highest total aldehyde emissions in cooking methods were produced by deep frying, followed by pan frying then by stir frying. Sunflower oil had the highest emissions of total aldehydes, regardless of cooking method and food type whereas rapeseed oil and palm oil had relatively lower emissions. This study suggests that using gentle cooking methods (e.g., stir frying) and using oils low in unsaturated fatty acids (e.g., palm oil or rapeseed oil) can reduce the production of aldehydes in COFs, especially long-chain aldehydes such as hexanal and t,t-2,4-DDE. Copyright © 2016 Elsevier B.V. All rights reserved.

Enzymatic oxidation of 2-phenylethylamine to phenylacetic acid and 2-phenylethanol with special reference to the metabolism of its intermediate phenylacetaldehyde.

PubMed

Panoutsopoulos, Georgios I; Kouretas, Demetrios; Gounaris, Elias G; Beedham, Christine

2004-12-01

2-phenylethylamine is an endogenous constituent of the human brain and is implicated in cerebral transmission. This bioactive amine is also present in certain foodstuffs such as chocolate, cheese and wine and may cause undesirable side effects in susceptible individuals. Metabolism of 2-phenylethylamine to phenylacetaldehyde is catalysed by monoamine oxidase B but the oxidation to its acid is usually ascribed to aldehyde dehydrogenase and the contribution of aldehyde oxidase and xanthine oxidase, if any, is ignored. The objective of this study was to elucidate the role of the molybdenum hydroxylases, aldehyde oxidase and xanthine oxidase, in the metabolism of phenylacetaldehyde derived from its parent biogenic amine. Treatments of 2-phenylethylamine with monoamine oxidase were carried out for the production of phenylacetaldehyde, as well as treatments of synthetic or enzymatic-generated phenylacetaldehyde with aldehyde oxidase, xanthine oxidase and aldehyde dehydrogenase. The results indicated that phenylacetaldehyde is metabolised mainly to phenylacetic acid with lower concentrations of 2-phenylethanol by all three oxidising enzymes. Aldehyde dehydrogenase was the predominant enzyme involved in phenylacetaldehyde oxidation and thus it has a major role in 2-phenylethylamine metabolism with aldehyde oxidase playing a less prominent role. Xanthine oxidase does not contribute to the oxidation of phenylacetaldehyde due to low amounts being present in guinea pig. Thus aldehyde dehydrogenase is not the only enzyme oxidising xenobiotic and endobiotic aldehydes and the role of aldehyde oxidase in such reactions should not be ignored.

[Pollution Characteristics of Aldehydes and Ketones Compounds in the Exhaust of Beijing Typical Restaurants].

PubMed

Cheng, Jing-chen; Cui, Tong; He, Wan-qing; Nie, Lei; Wang, Jun-ling; Pan, Tao

2015-08-01

Aldehydes and ketones compounds, as one of the components in the exhaust of restaurants, are a class of volatile organic compounds (VOCs) with strong chemical reactivity. However, there is no systematic study on aldehydes and ketones compounds in the exhaust of restaurants. To further clarify the food source emission levels of aldehydes and ketones compounds and controlling measures, to access city group catering VOCs emissions control decision-making basis, this study selected 8 Beijing restaurants with different types. The aldehydes and ketones compounds were sampled using DNPH-silica tube, and then ultra performance liquid chromatography was used for quantitative measurement. The aldehydes and ketones concentrations of reference volume condition from 8 restaurants in descending order were Roasted Duck restaurant, Chinese Style Barbecue, Home Dishes, Western Fast-food, School Canteen, Chinese Style Fast-food, Sichuan Cuisine, Huaiyang Cuisine. The results showed that the range of aldehydes and ketones compounds (C1-C9) concentrations of reference volume condition in the exhaust of restaurants was 115.47-1035.99 microg x m(-3). The composition of aldehydes and ketones compounds in the exhaust of sampled restaurants was obviously different. The percentages of C1-C3 were above 40% in the exhaust from Chinese style restaurants. Fast food might emit more C4-C9 aldehydes and ketones compounds. From the current situation of existing aldehydes and ketones compounds control, the removal efficiency of high voltage electrostatic purifiers widely used in Beijing is limited.

Hydrogen Sulfide Ameliorates Homocysteine-Induced Cognitive Dysfunction by Inhibition of Reactive Aldehydes Involving Upregulation of ALDH2.

PubMed

Li, Min; Zhang, Ping; Wei, Hai-Jun; Li, Man-Hong; Zou, Wei; Li, Xiang; Gu, Hong-Feng; Tang, Xiao-Qing

2017-04-01

Homocysteine, a risk factor for Alzheimer's disease, induces cognitive dysfunction. Reactive aldehydes play an important role in cognitive dysfunction. Aldehyde-dehydrogenase 2 detoxifies reactive aldehydes. Hydrogen sulfide, a novel neuromodulator, has neuroprotective effects and regulates learning and memory. Our previous work confirmed that the disturbance of hydrogen sulfide synthesis is invovled in homocysteine-induced defects in learning and memory. Therefore, the present work was to explore whether hydrogen sulfide ameliorates homocysteine-generated cognitive dysfunction and to investigate whether its underlying mechanism is related to attenuating accumulation of reactive aldehydes by upregulation of aldehyde-dehydrogenase 2. The cognitive function of rats was assessed by the Morris water maze test and the novel object recognition test. The levels of malondialdehyde, 4-hydroxynonenal, and glutathione as well as the activity of aldehyde-dehydrogenase 2 were determined by enzyme linked immunosorbent assay; the expression of aldehyde-dehydrogenase 2 was detected by western blot. The behavior experiments, Morris water maze test and novel objects recognition test, showed that homocysteine induced deficiency in learning and memory in rats, and this deficiency was reversed by treatment of NaHS (a donor of hydrogen sulfide). We demonstrated that NaHS inhibited homocysteine-induced increases in generations of MDA and 4-HNE in the hippocampus of rats and that hydrogen sulfide reversed homocysteine-induced decreases in the level of glutathione as well as the activity and expression of aldehyde-dehydrogenase 2 in the hippocampus of rats. Hydrogen sulfide ameliorates homocysteine-induced impairment in cognitive function by decreasing accumulation of reactive aldehydes as a result of upregulations of glutathione and aldehyde-dehydrogenase 2. © The Author 2016. Published by Oxford University Press on behalf of CINP.

Hydrogen Sulfide Ameliorates Homocysteine-Induced Cognitive Dysfunction by Inhibition of Reactive Aldehydes Involving Upregulation of ALDH2

PubMed Central

Li, Min; Zhang, Ping; Wei, Hai-jun; Li, Man-Hong; Li, Xiang; Gu, Hong-Feng

2017-01-01

Abstract Background: Homocysteine, a risk factor for Alzheimer’s disease, induces cognitive dysfunction. Reactive aldehydes play an important role in cognitive dysfunction. Aldehyde-dehydrogenase 2 detoxifies reactive aldehydes. Hydrogen sulfide, a novel neuromodulator, has neuroprotective effects and regulates learning and memory. Our previous work confirmed that the disturbance of hydrogen sulfide synthesis is invovled in homocysteine-induced defects in learning and memory. Therefore, the present work was to explore whether hydrogen sulfide ameliorates homocysteine-generated cognitive dysfunction and to investigate whether its underlying mechanism is related to attenuating accumulation of reactive aldehydes by upregulation of aldehyde-dehydrogenase 2. Methods: The cognitive function of rats was assessed by the Morris water maze test and the novel object recognition test. The levels of malondialdehyde, 4-hydroxynonenal, and glutathione as well as the activity of aldehyde-dehydrogenase 2 were determined by enzyme linked immunosorbent assay; the expression of aldehyde-dehydrogenase 2 was detected by western blot. Results: The behavior experiments, Morris water maze test and novel objects recognition test, showed that homocysteine induced deficiency in learning and memory in rats, and this deficiency was reversed by treatment of NaHS (a donor of hydrogen sulfide). We demonstrated that NaHS inhibited homocysteine-induced increases in generations of MDA and 4-HNE in the hippocampus of rats and that hydrogen sulfide reversed homocysteine-induced decreases in the level of glutathione as well as the activity and expression of aldehyde-dehydrogenase 2 in the hippocampus of rats. Conclusion: Hydrogen sulfide ameliorates homocysteine-induced impairment in cognitive function by decreasing accumulation of reactive aldehydes as a result of upregulations of glutathione and aldehyde-dehydrogenase 2. PMID:27988490

Increased salivary aldehyde dehydrogenase 1 in non-reticular oral lichen planus*

PubMed Central

Mansourian, Arash; Shanbehzadeh, Najmeh; Kia, Seyed Javad; Moosavi, Mahdieh-Sadat

2017-01-01

Background Oral lichen planus is a potentially malignant disorder. One of the malignant transformation markers is cancer stem cells. One of the proposed marker for the detection of cancer stem cells's in head and neck cancer is aldehyde dehydrogenase. Recently it is shown that aldehyde dehydrogenase 1 expression in tissue samples is associated with oral lichen planus malignant transformation. Objective This study evaluates salivary aldehyde dehydrogenase 1 in oral lichen planus. Method Thirty patients and 30 age and sex-matched healthy volunteers were recruited. Oral lichen planus was diagnosed based on the modified World Health Organization criteria. Subjects in the case group were divided into reticular and non-reticular forms. Unstimulated salivary samples were collected at 10-12 AM. Saliva concentrations of aldehyde dehydrogenase 1 were measured by ELISA. Results The differences between aldehyde dehydrogenase levels in the oral lichen planus group compared with the control group were not significant but aldehyde dehydrogenase in non-reticular oral lichen planus was significantly higher than that of the reticular form. Limitations of the study This is a cross-sectional study, thus longitudinal studies in oral lichen planus may present similar or different results. Conclusions The mechanism of malignant transformation in oral lichen planus is not defined. Previous analyses revealed that the aldehyde dehydrogenase 1 expression is significantly correlated with increased risk of transformation. This finding is consistent with our results because in the erosive and ulcerative forms of oral lichen planus, which have an increased risk of transformation, salivary aldehyde dehydrogenase 1 was overexpressed. A higher salivary aldehyde dehydrogenase level in non-reticular oral lichen planus can be a defensive mechanism against higher oxidative stress in these groups. Aldehyde dehydrogenase may be one of the malignant transformation markers in oral lichen planus. Further studies are needed for introducing aldehyde dehydrogenase as a prognostic indicator in certain lesions. PMID:28538873

Five Fatty Aldehyde Dehydrogenase Enzymes from Marinobacter and Acinetobacter spp. and Structural Insights into the Aldehyde Binding Pocket

PubMed Central

Bertram, Jonathan H.; Mulliner, Kalene M.; Shi, Ke; Plunkett, Mary H.; Nixon, Peter; Serratore, Nicholas A.; Douglas, Christopher J.; Aihara, Hideki

2017-01-01

ABSTRACT Enzymes involved in lipid biosynthesis and metabolism play an important role in energy conversion and storage and in the function of structural components such as cell membranes. The fatty aldehyde dehydrogenase (FAldDH) plays a central function in the metabolism of lipid intermediates, oxidizing fatty aldehydes to the corresponding fatty acid and competing with pathways that would further reduce the fatty aldehydes to fatty alcohols or require the fatty aldehydes to produce alkanes. In this report, the genes for four putative FAldDH enzymes from Marinobacter aquaeolei VT8 and an additional enzyme from Acinetobacter baylyi were heterologously expressed in Escherichia coli and shown to display FAldDH activity. Five enzymes (Maqu_0438, Maqu_3316, Maqu_3410, Maqu_3572, and the enzyme reported under RefSeq accession no. WP_004927398) were found to act on aldehydes ranging from acetaldehyde to hexadecanal and also acted on the unsaturated long-chain palmitoleyl and oleyl aldehydes. A comparison of the specificities of these enzymes with various aldehydes is presented. Crystallization trials yielded diffraction-quality crystals of one particular FAldDH (Maqu_3316) from M. aquaeolei VT8. Crystals were independently treated with both the NAD+ cofactor and the aldehyde substrate decanal, revealing specific details of the likely substrate binding pocket for this class of enzymes. A likely model for how catalysis by the enzyme is accomplished is also provided. IMPORTANCE This study provides a comparison of multiple enzymes with the ability to oxidize fatty aldehydes to fatty acids and provides a likely picture of how the fatty aldehyde and NAD+ are bound to the enzyme to facilitate catalysis. Based on the information obtained from this structural analysis and comparisons of specificities for the five enzymes that were characterized, correlations to the potential roles played by specific residues within the structure may be drawn. PMID:28389542

Five Fatty Aldehyde Dehydrogenase Enzymes from Marinobacter and Acinetobacter spp. and Structural Insights into the Aldehyde Binding Pocket

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bertram, Jonathan H.; Mulliner, Kalene M.; Shi, Ke

ABSTRACT Enzymes involved in lipid biosynthesis and metabolism play an important role in energy conversion and storage and in the function of structural components such as cell membranes. The fatty aldehyde dehydrogenase (FAldDH) plays a central function in the metabolism of lipid intermediates, oxidizing fatty aldehydes to the corresponding fatty acid and competing with pathways that would further reduce the fatty aldehydes to fatty alcohols or require the fatty aldehydes to produce alkanes. In this report, the genes for four putative FAldDH enzymes fromMarinobacter aquaeoleiVT8 and an additional enzyme fromAcinetobacter baylyiwere heterologously expressed inEscherichia coliand shown to display FAldDH activity.more » Five enzymes (Maqu_0438, Maqu_3316, Maqu_3410, Maqu_3572, and the enzyme reported under RefSeq accession no.WP_004927398) were found to act on aldehydes ranging from acetaldehyde to hexadecanal and also acted on the unsaturated long-chain palmitoleyl and oleyl aldehydes. A comparison of the specificities of these enzymes with various aldehydes is presented. Crystallization trials yielded diffraction-quality crystals of one particular FAldDH (Maqu_3316) fromM. aquaeoleiVT8. Crystals were independently treated with both the NAD +cofactor and the aldehyde substrate decanal, revealing specific details of the likely substrate binding pocket for this class of enzymes. A likely model for how catalysis by the enzyme is accomplished is also provided. IMPORTANCEThis study provides a comparison of multiple enzymes with the ability to oxidize fatty aldehydes to fatty acids and provides a likely picture of how the fatty aldehyde and NAD +are bound to the enzyme to facilitate catalysis. Based on the information obtained from this structural analysis and comparisons of specificities for the five enzymes that were characterized, correlations to the potential roles played by specific residues within the structure may be drawn.« less

Molecular Mechanisms of Aldehyde Toxicity: A Chemical Perspective

PubMed Central

2015-01-01

Aldehydes are electrophilic compounds to which humans are pervasively exposed. Despite a significant health risk due to exposure, the mechanisms of aldehyde toxicity are poorly understood. This ambiguity is likely due to the structural diversity of aldehyde derivatives and corresponding differences in chemical reactions and biological targets. To gain mechanistic insight, we have used parameters based on the hard and soft, acids and bases (HSAB) theory to profile the different aldehyde subclasses with respect to electronic character (softness, hardness), electrophilic reactivity (electrophilic index), and biological nucleophilic targets. Our analyses indicate that short chain aldehydes and longer chain saturated alkanals are hard electrophiles that cause toxicity by forming adducts with hard biological nucleophiles, e.g., primary nitrogen groups on lysine residues. In contrast, α,β-unsaturated carbonyl derivatives, alkenals, and the α-oxoaldehydes are soft electrophiles that preferentially react with soft nucleophilic thiolate groups on cysteine residues. The aldehydes can therefore be grouped into subclasses according to common electronic characteristics (softness/hardness) and molecular mechanisms of toxicity. As we will discuss, the toxic potencies of these subgroups are generally related to corresponding electrophilicities. For some aldehydes, however, predictions of toxicity based on electrophilicity are less accurate due to inherent physicochemical variables that limit target accessibility, e.g., steric hindrance and solubility. The unsaturated aldehydes are also members of the conjugated type-2 alkene chemical class that includes α,β-unsaturated amide, ketone, and ester derivatives. Type-2 alkenes are electrophiles of varying softness and electrophilicity that share a common mechanism of toxicity. Therefore, exposure to an environmental mixture of unsaturated carbonyl derivatives could cause “type-2 alkene toxicity” through additive interactions. Finally, we propose that environmentally derived aldehydes can accelerate diseases by interacting with endogenous aldehydes generated during oxidative stress. This review provides a basis for understanding aldehyde mechanisms and environmental toxicity through the context of electronic structure, electrophilicity, and nucleophile target selectivity. PMID:24911545

Crude glycerol combustion: Particulate, acrolein, other volatile organic emissions

EPA Science Inventory

This STICS entry is for the presentation materials for a peer-reviewed journal manuscript entry by the same title (ORD-000108) previously entered an approved. A Product Description / Abstract for ORD-000108 was previously entered.

Chemical characterization of the smokes of selected US commercial cigarettes: tar, nicotine, carbon monoxide, oxides of nitrogen, hydrogen cyanide, and acrolein. [32 brands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jenkins, R.A.; White, S.K.; Griest, W.H.

Thirty-two brands of US commercial cigarettes were analyzed for their deliveries of tar, nicotine, CO, CO/sub 2/, HCN, NO/sub x/, and acrolein under standard smoking conditions. Per cigarette and per puff deliveries were calculated. The sample suite contained filtered and non-filtered varieties, and relatively popular high, low, and medium tar delivery cigarettes. The range of deliveries of these constituents was considerable. Statistical analysis indicated that the deliveries of nicotine, CO, NO/sub x/, and HCN could usually be estimated to within 50% of their actual delivery if the tar delivery was known. However, brand to brand variation in the constituent ratiosmore » was sufficient so as to preclude the exact calculation of the delivery of one component from that of another.« less

Biosynthesis of mercapturic acids from allyl alcohol, allyl esters and acrolein

PubMed Central

Kaye, Clive M.

1973-01-01

1. 3-Hydroxypropylmercapturic acid, i.e. N-acetyl-S-(3-hydroxypropyl)-l-cysteine, was isolated, as its dicyclohexylammonium salt, from the urine of rats after the subcutaneous injection of each of the following compounds: allyl alcohol, allyl formate, allyl propionate, allyl nitrate, acrolein and S-(3-hydroxypropyl)-l-cysteine. 2. Allylmercapturic acid, i.e. N-acetyl-S-allyl-l-cysteine, was isolated from the urine of rats after the subcutaneous injection of each of the following compounds: triallyl phosphate, sodium allyl sulphate and allyl nitrate. The sulphoxide of allylmercapturic acid was detected in the urine excreted by these rats. 3. 3-Hydroxypropylmercapturic acid was identified by g.l.c. as a metabolite of allyl acetate, allyl stearate, allyl benzoate, diallyl phthalate, allyl nitrite, triallyl phosphate and sodium allyl sulphate. 4. S-(3-Hydroxypropyl)-l-cysteine was detected in the bile of a rat dosed with allyl acetate. PMID:4762754

Medium-chain dehydrogenase/reductase and aldo-keto reductase scavenge reactive carbonyls in Synechocystis sp. PCC 6803.

PubMed

Shimakawa, Ginga; Kohara, Ayaka; Miyake, Chikahiro

2018-03-01

Reactive carbonyls (RCs), which are inevitably produced during respiratory and photosynthetic metabolism, have the potential to cause oxidative damage to photosynthetic organisms. Previously, we proposed a scavenging model for RCs in the cyanobacterium Synechocystis sp. PCC 6803 (S. 6803). In the current study, we constructed mutants deficient in the enzymes medium-chain dehydrogenase/reductase (ΔMDR) and aldo-keto reductase (ΔAKR) to investigate their contributions to RC scavenging in vivo. We found that treatment with the lipid-derived RC acrolein causes growth inhibition and promotes greater protein carbonylation in ΔMDR, compared with the wild-type and ΔAKR. In both ΔMDR and ΔAKR, photosynthesis is severely inhibited in the presence of acrolein. These results suggest that these enzymes function as part of the scavenging systems for RCs in S. 6803 in vivo. © 2018 Federation of European Biochemical Societies.

Biogenic Aldehydes as Therapeutic Targets for Cardiovascular Disease

PubMed Central

Nelson, Margaret-Ann M; Baba, Shahid P; Andersonc, Ethan J

2017-01-01

Aldehydes are continuously formed in biological systems through enzyme-dependent and spontaneous oxidation of lipids, glucose, and primary amines. These highly reactive, biogenic electrophiles can become toxic via covalent modification of proteins, lipids and DNA. Thus, agents that scavenge aldehydes through conjugation have therapeutic value for a number of major cardiovascular diseases. Several commonly-prescribed drugs (e.g., hydralazine) have been shown to have potent aldehyde-conjugating properties which may contribute to their beneficial effects. Herein, we briefly describe the major sources and toxicities of biogenic aldehydes in cardiovascular system, and provide an overview of drugs that are known to have aldehyde-conjugating effects. Some compounds of phytochemical origin, and histidyl-dipeptides with emerging therapeutic value in this area are also discussed. PMID:28528297

40 CFR 92.109 - Analyzer specifications.

Code of Federal Regulations, 2014 CFR

2014-07-01

... and Aldehydes. The sampling and analysis procedures for alcohols and aldehydes, where applicable... alcohols and aldehydes, and with good engineering practice. (4) Other methods of measuring organics that...

40 CFR 92.109 - Analyzer specifications.

Code of Federal Regulations, 2011 CFR

2011-07-01

... and Aldehydes. The sampling and analysis procedures for alcohols and aldehydes, where applicable... alcohols and aldehydes, and with good engineering practice. (4) Other methods of measuring organics that...

40 CFR 92.109 - Analyzer specifications.

Code of Federal Regulations, 2012 CFR

2012-07-01

... and Aldehydes. The sampling and analysis procedures for alcohols and aldehydes, where applicable... alcohols and aldehydes, and with good engineering practice. (4) Other methods of measuring organics that...

40 CFR 92.109 - Analyzer specifications.

Code of Federal Regulations, 2013 CFR

2013-07-01

... and Aldehydes. The sampling and analysis procedures for alcohols and aldehydes, where applicable... alcohols and aldehydes, and with good engineering practice. (4) Other methods of measuring organics that...

40 CFR 92.109 - Analyzer specifications.

Code of Federal Regulations, 2010 CFR

2010-07-01

... and Aldehydes. The sampling and analysis procedures for alcohols and aldehydes, where applicable... alcohols and aldehydes, and with good engineering practice. (4) Other methods of measuring organics that...

Aromatic aldehydes at the active site of aldehyde oxidoreductase from Desulfovibrio gigas: reactivity and molecular details of the enzyme-substrate and enzyme-product interaction.

PubMed

Correia, Hugo D; Marangon, Jacopo; Brondino, Carlos D; Moura, Jose J G; Romão, Maria J; González, Pablo J; Santos-Silva, Teresa

2015-03-01

Desulfovibrio gigas aldehyde oxidoreductase (DgAOR) is a mononuclear molybdenum-containing enzyme from the xanthine oxidase (XO) family, a group of enzymes capable of catalyzing the oxidative hydroxylation of aldehydes and heterocyclic compounds. The kinetic studies reported in this work showed that DgAOR catalyzes the oxidative hydroxylation of aromatic aldehydes, but not heterocyclic compounds. NMR spectroscopy studies using (13)C-labeled benzaldehyde confirmed that DgAOR catalyzes the conversion of aldehydes to the respective carboxylic acids. Steady-state kinetics in solution showed that high concentrations of the aromatic aldehydes produce substrate inhibition and in the case of 3-phenyl propionaldehyde a suicide substrate behavior. Hydroxyl-substituted aromatic aldehydes present none of these behaviors but the kinetic parameters are largely affected by the position of the OH group. High-resolution crystallographic structures obtained from single crystals of active-DgAOR soaked with benzaldehyde showed that the side chains of Phe425 and Tyr535 are important for the stabilization of the substrate in the active site. On the other hand, the X-ray data of DgAOR soaked with trans-cinnamaldehyde showed a cinnamic acid molecule in the substrate channel. The X-ray data of DgAOR soaked with 3-phenyl propionaldehyde showed clearly how high substrate concentrations inactivate the enzyme by binding covalently at the surface of the enzyme and blocking the substrate channel. The different reactivity of DgAOR versus aldehyde oxidase and XO towards aromatic aldehydes and N-heterocyclic compounds is explained on the basis of the present kinetic and structural data.

Dose-dependent DNA adduct formation by cinnamaldehyde and other food-borne α,β-unsaturated aldehydes predicted by physiologically based in silico modelling.

PubMed

Kiwamoto, R; Ploeg, D; Rietjens, I M C M; Punt, A

2016-03-01

Genotoxicity of α,β-unsaturated aldehydes shown in vitro raises a concern for the use of the aldehydes as food flavourings, while at low dose exposures the formation of DNA adducts may be prevented by detoxification. Unlike many α,β-unsaturated aldehydes for which in vivo data are absent, cinnamaldehyde was shown to be not genotoxic or carcinogenic in vivo. The present study aimed at comparing dose-dependent DNA adduct formation by cinnamaldehyde and 18 acyclic food-borne α,β-unsaturated aldehydes using physiologically based kinetic/dynamic (PBK/D) modelling. In rats, cinnamaldehyde was predicted to induce higher DNA adducts levels than 6 out of the 18 α,β-unsaturated aldehydes, indicating that these 6 aldehydes may also test negative in vivo. At the highest cinnamaldehyde dose that tested negative in vivo, cinnamaldehyde was predicted to form at least three orders of magnitude higher levels of DNA adducts than the 18 aldehydes at their respective estimated daily intake. These results suggest that for all the 18 α,β-unsaturated aldehydes DNA adduct formation at doses relevant for human dietary exposure may not raise a concern. The present study illustrates a possible use of physiologically based in silico modelling to facilitate a science-based comparison and read-across on the possible risks posed by DNA reactive agents. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparative Computational Modeling of Airflows and Vapor Dosimetry in the Respiratory Tracts of Rat, Monkey, and Human

PubMed Central

Corley, Richard A.

2012-01-01

Computational fluid dynamics (CFD) models are useful for predicting site-specific dosimetry of airborne materials in the respiratory tract and elucidating the importance of species differences in anatomy, physiology, and breathing patterns. We improved the imaging and model development methods to the point where CFD models for the rat, monkey, and human now encompass airways from the nose or mouth to the lung. A total of 1272, 2172, and 135 pulmonary airways representing 17±7, 19±9, or 9±2 airway generations were included in the rat, monkey and human models, respectively. A CFD/physiologically based pharmacokinetic model previously developed for acrolein was adapted for these anatomically correct extended airway models. Model parameters were obtained from the literature or measured directly. Airflow and acrolein uptake patterns were determined under steady-state inhalation conditions to provide direct comparisons with prior data and nasal-only simulations. Results confirmed that regional uptake was sensitive to airway geometry, airflow rates, acrolein concentrations, air:tissue partition coefficients, tissue thickness, and the maximum rate of metabolism. Nasal extraction efficiencies were predicted to be greatest in the rat, followed by the monkey, and then the human. For both nasal and oral breathing modes in humans, higher uptake rates were predicted for lower tracheobronchial tissues than either the rat or monkey. These extended airway models provide a unique foundation for comparing material transport and site-specific tissue uptake across a significantly greater range of conducting airways in the rat, monkey, and human than prior CFD models. PMID:22584687

Cationic uremic toxins affect human renal proximal tubule cell functioning through interaction with the organic cation transporter.

PubMed

Schophuizen, Carolien M S; Wilmer, Martijn J; Jansen, Jitske; Gustavsson, Lena; Hilgendorf, Constanze; Hoenderop, Joost G J; van den Heuvel, Lambert P; Masereeuw, Rosalinde

2013-12-01

Several organic cations, such as guanidino compounds and polyamines, have been found to accumulate in plasma of patients with kidney failure due to inadequate renal clearance. Here, we studied the interaction of cationic uremic toxins with renal organic cation transport in a conditionally immortalized human proximal tubule epithelial cell line (ciPTEC). Transporter activity was measured and validated in cell suspensions by studying uptake of the fluorescent substrate 4-(4-(dimethylamino)styryl)-N-methylpyridinium-iodide (ASP(+)). Subsequently, the inhibitory potencies of the cationic uremic toxins, cadaverine, putrescine, spermine and spermidine (polyamines), acrolein (polyamine breakdown product), guanidine, and methylguanidine (guanidino compounds) were determined. Concentration-dependent inhibition of ASP(+) uptake by TPA, cimetidine, quinidine, and metformin confirmed functional endogenous organic cation transporter 2 (OCT2) expression in ciPTEC. All uremic toxins tested inhibited ASP(+) uptake, of which acrolein required the lowest concentration to provoke a half-maximal inhibition (IC50 = 44 ± 2 μM). A Dixon plot was constructed for acrolein using three independent inhibition curves with 10, 20, or 30 μM ASP(+), which demonstrated competitive or mixed type of interaction (K i = 93 ± 16 μM). Exposing the cells to a mixture of cationic uremic toxins resulted in a more potent and biphasic inhibitory response curve, indicating complex interactions between the toxins and ASP(+) uptake. In conclusion, ciPTEC proves a suitable model to study cationic xenobiotic interactions. Inhibition of cellular uptake transport was demonstrated for several uremic toxins, which might indicate a possible role in kidney disease progression during uremia.

40 CFR 92.132 - Calculations.

Code of Federal Regulations, 2012 CFR

2012-07-01

...=Aldehydes grams/BHP-hr=MAL mode/Measured BHP in mode. (vii) EAL mode=Aldehydes grams/BHP-hr=MAL mode/Measured BHP in mode. Where: MAL mode=Total aldehyde mass emissions (grams per hour) for each test mode. (2... mode=(DCH2O/106)30.026(DVol)/Vm MCH2O mode=(WCH2O/106)30.026(WVol)/Vm (1) If aldehydes are measured...

40 CFR 92.132 - Calculations.

Code of Federal Regulations, 2010 CFR

2010-07-01

...=Aldehydes grams/BHP-hr=MAL mode/Measured BHP in mode. (vii) EAL mode=Aldehydes grams/BHP-hr=MAL mode/Measured BHP in mode. Where: MAL mode=Total aldehyde mass emissions (grams per hour) for each test mode. (2... mode=(DCH2O/106)30.026(DVol)/Vm MCH2O mode=(WCH2O/106)30.026(WVol)/Vm (1) If aldehydes are measured...

40 CFR 92.132 - Calculations.

Code of Federal Regulations, 2014 CFR

2014-07-01

...=Aldehydes grams/BHP-hr=MAL mode/Measured BHP in mode. (vii) EAL mode=Aldehydes grams/BHP-hr=MAL mode/Measured BHP in mode. Where: MAL mode=Total aldehyde mass emissions (grams per hour) for each test mode. (2... mode=(DCH2O/106)30.026(DVol)/Vm MCH2O mode=(WCH2O/106)30.026(WVol)/Vm (1) If aldehydes are measured...

40 CFR 92.132 - Calculations.

Code of Federal Regulations, 2011 CFR

2011-07-01

...=Aldehydes grams/BHP-hr=MAL mode/Measured BHP in mode. (vii) EAL mode=Aldehydes grams/BHP-hr=MAL mode/Measured BHP in mode. Where: MAL mode=Total aldehyde mass emissions (grams per hour) for each test mode. (2... mode=(DCH2O/106)30.026(DVol)/Vm MCH2O mode=(WCH2O/106)30.026(WVol)/Vm (1) If aldehydes are measured...

40 CFR 92.132 - Calculations.

Code of Federal Regulations, 2013 CFR

2013-07-01

...=Aldehydes grams/BHP-hr=MAL mode/Measured BHP in mode. (vii) EAL mode=Aldehydes grams/BHP-hr=MAL mode/Measured BHP in mode. Where: MAL mode=Total aldehyde mass emissions (grams per hour) for each test mode. (2... mode=(DCH2O/106)30.026(DVol)/Vm MCH2O mode=(WCH2O/106)30.026(WVol)/Vm (1) If aldehydes are measured...

Cinnamic aldehyde: a survey of consumer patch-test sensitization.

PubMed

Danneman, P J; Booman, K A; Dorsky, J; Kohrman, K A; Rothenstein, A S; Sedlak, R I; Steltenkamp, R J; Thompson, G R

1983-12-01

The potential for cinnamic aldehyde, an important fragrance and flavour ingredient, to induce or to elicit delayed contact hypersensitivity reactions in man was evaluated by analysing patch-test data. Results of studies involving a total of 4117 patch tests on various consumer products and fragrance blends containing cinnamic aldehyde and on the material itself were collected from fragrance and formulator companies. The data indicate that cinnamic aldehyde contained in consumer products and fragrance blends at concentrations up to 6 X 10(-1)%, and patch-tested at concentrations up to 8 X 10(-3)%, has no detectable potential to induce hypersensitivity. Cinnamic aldehyde when tested alone induced a dose-related hypersensitivity response. According to published reports, cinnamic aldehyde elicited positive delayed hypersensitivity responses in dermatitic patients. However, results of the current survey show that when cinnamic aldehyde was tested alone or as part of a mixture in subjects in the general population, no pre-existing hypersensitivity reactions to the fragrance material were observed in any of the 4117 patch tests which constituted the survey. Cinnamic aldehyde at the concentrations contained in consumer products and fragrances, has a very low potential to induce hypersensitivity ('induced' reactions) or to elicit sensitization reactions ('elicited' reactions) in the general population.

Release and Formation of Oxidation-Related Aldehydes during Wine Oxidation.

PubMed

Bueno, Mónica; Carrascón, Vanesa; Ferreira, Vicente

2016-01-27

Twenty-four Spanish wines were subjected to five consecutive cycles of air saturation at 25 °C. Free and bound forms of carbonyls were measured in the initial samples and after each saturation. Nonoxidized commercial wines contain important and sensory relevant amounts of oxidation-related carbonyls under the form of odorless bound forms. Models relating the contents in total aldehydes to the wine chemical composition suggest that fermentation can be a major origin for Strecker aldehydes: methional, phenylacetaldehyde, isobutyraldehyde, 2-methylbutanal, and isovaleraldehyde. Bound forms are further cleaved, releasing free aldehydes during the first steps of wine oxidation, as a consequence of equilibrium shifts caused by the depletion of SO2. At low levels of free SO2, de novo formation and aldehyde degradation are both observed. The relative importance of these phenomena depends on both the aldehyde and the wine. Models relating aldehyde formation rates to wine chemical composition suggest that amino acids are in most cases the most important precursors for de novo formation.

Biogenic Aldehydes as Therapeutic Targets for Cardiovascular Disease.

PubMed

Nelson, Margaret-Ann M; Baba, Shahid P; Anderson, Ethan J

2017-04-01

Aldehydes are continuously formed in biological systems through enzyme-dependent and spontaneous oxidation of lipids, glucose, and primary amines. These highly reactive, biogenic electrophiles can become toxic via covalent modification of proteins, lipids and DNA. Thus, agents that scavenge aldehydes through conjugation have therapeutic value for a number of major cardiovascular diseases. Several commonly-prescribed drugs (e.g., hydralazine) have been shown to have potent aldehyde-conjugating properties which may contribute to their beneficial effects. Herein, we briefly describe the major sources and toxicities of biogenic aldehydes in cardiovascular system, and provide an overview of drugs that are known to have aldehyde-conjugating effects. Some compounds of phytochemical origin, and histidyl-dipeptides with emerging therapeutic value in this area are also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

n-Aldehydes (C6-C10) in snow samples collected at the high alpine research station Jungfraujoch during CLACE 5

NASA Astrophysics Data System (ADS)

Sieg, K.; Starokozhev, E.; Fries, E.; Sala, S.; Püttmann, W.

2009-04-01

C6-C10 n-aldehydes were analyzed in samples of freshly fallen snow collected at the high alpine research station Jungfraujoch, Switzerland, during the Cloud and Aerosol Characterization Experiments (CLACE) 5 in February and March 2006. Sampling was carried out on the Sphinx platform. Headspace - solid phase dynamic extraction (HS-SPDE) combined with gas chromatography/mass spectrometry (GC/MS) was used to quantify n-aldehydes in melted snow samples. n-Hexanal was identified as the most abundant n-aldehyde (median concentration 1.324 µg L-1) followed by n-nonanal, n-decanal, n-octanal and n-heptanal (median concentrations 1.239, 0.863, 0.460 and 0.304 µg L-1, respectively). A wide range of concentrations of n-aldehydes was found in snow samples from Jungfraujoch, even for samples collected at the same time during the same snowfall event. According to their physical and chemical characteristics, n-aldehydes are expected to be primarily linked to aerosol particles in the atmosphere suggesting the uptake of n-aldehydes into snow via the particle phase. Particle scavenging can occur during snow formation in clouds. The high concentration variations of the n-aldehydes among the snow samples can be explained assuming that aerosol particles, which are loaded with n-aldehydes, are heterogeneously distributed throughout the snow samples. Higher median concentrations of all n-aldehydes were observed when air masses reached Jungfraujoch from the north-northwest in comparison to air masses arriving from the southeast-southwest. The sources of atmospheric n-aldehydes present at Jungfraujoch are most likely to be related to direct and indirect biogenic emissions. The presence of n-aldehydes as semivolatile constituents of direct biogenic emissions from vegetation has been reported previously in studies of Ciccioli et al. [1], Yokouchi et al. [2] and Kesselmeier and Staudt [3]. The distribution pattern of the n-aldehydes in emissions from vegetation largely matches with the n-aldehyde pattern found in snow collected at Jungfraujoch. One exception is the significantly higher proportion of n-hexanal in the Jungfraujoch samples compared to vegetation emission. Additionally, indirect biogenic emissions can contribute to the atmospheric concentrations of n-aldehydes through oxidation of precursor compounds of biogenic origin. In this context, Moise and Rudich [4] and Thornberry and Abbatt [5] proposed the preferential formation of n-nonanal and n-hexanal from the cleavage by ozonolysis of double bonds in unsaturated fatty acids (namely oleic acid and linoleic acids). The predominance of n-hexanal and n-nonanal among the C6-C10 n-aldehydes in the snow samples collected at Jungfraujoch during CLACE 5 is therefore an argument for the formation of the aldehydes through oxidation of unsaturated fatty acids in the atmosphere. Anthropogenic emissions of n-aldehydes i.e. from fossil fuel burning are thought to be negligible in the air masses reaching Jungfraujoch. References: [1] P. Ciccioli, E. Brancaleoni, M. Frattoni, A. Cecinato, A. Brachetti, Atmos. Environ., Part A 27 (1993) 1891. [2] Y. Yokouchi, H. Mukai, K. Nakajima, Y. Ambe, Atmos. Environ., Part A 24 (1990) 439. [3] J. Kesselmeier, M. Staudt, J. Atmos. Chem. 33 (1999) 23. [4] T. Moise, Y. Rudich, J. Phys. Chem. 106 (2002) 6469. [5] T. Thornberry, J.P.D. Abbatt, Phys. Chem. Chem. Phys. 6 (2004) 84.

Chiral Brønsted Acid-Catalyzed Allylboration of Aldehydes

PubMed Central

Jain, Pankaj; Antilla, Jon C.

2010-01-01

The catalytic enantioselective allylation of aldehydes is a long-standing problem with considerable interest to the chemical community. We wish to disclose a new high yielding and highly enantioselective chiral Brønsted acid-catalyzed allylboration of aldehydes. The reaction is shown to be highly general, with broad substrate scope that covers aryl, heteroaryl, α,β-unsaturated, and aliphatic aldehydes. The reaction conditions were also shown to be effective for the catalytic enantioselective crotylation of aldehydes. We believe that the high reactivity of the allyl boronate is due to protonation of the boronate oxygen by the chiral phosphoric acid catalyst. PMID:20690662

Thiazolylidene-catalyzed cleavage of methyl oleate-derived α-hydroxy ketone to the corresponding free aldehydes.

PubMed

Deruer, Elsa; Duguet, Nicolas; Lemaire, Marc

2015-08-10

The thiazolylidene-catalyzed cleavage of the α-hydroxy ketone derived from methyl oleate gave the corresponding aldehydes under nonoxidative conditions through a retro-benzoin process. The aldehydes produced are in equilibrium with their corresponding acyloins. To illustrate the synthetic utility of this protocol, the aldehydes were recovered by distillation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fatty aldehyde dehydrogenases in Acinetobacter sp. strain HO1-N: role in hexadecanol metabolism.

PubMed Central

Singer, M E; Finnerty, W R

1985-01-01

The role of fatty aldehyde dehydrogenases (FALDHs) in hexadecane and hexadecanol metabolism was studied in Acinetobacter sp. strain HO1-N. Two distinct FALDHs were demonstrated in Acinetobacter sp. strain HO1-N: a membrane-bound, NADP-dependent FALDH activity induced 5-, 15-, and 9-fold by growth on hexadecanol, dodecyl aldehyde, and hexadecane, respectively, and a constitutive, NAD-dependent, membrane-localized FALDH. The NADP-dependent FALDH exhibited apparent Km and Vmax values for decyl aldehyde of 5.0, 13.0, 18.0, and 18.3 microM and 537.0, 500.0, 25.0, and 38.0 nmol/min in hexadecane-, hexadecanol-, ethanol-, palmitate-grown cells, respectively. FALDH isozymes ald-a, ald-b, and ald-c were demonstrated by gel electrophoresis in extracts of hexadecane- and hexadecanol-grown cells. ald-a, ald-b, and ald-d were present in dodecyl aldehyde-grown cells, while palmitate-grown control cells contained ald-b and ald-d. Dodecyl aldehyde-negative mutants were isolated and grouped into two phenotypic classes based on growth: class 1 mutants were hexadecane and hexadecanol negative and class 2 mutants were hexadecane and hexadecanol positive. Specific activity of NADP-dependent FALDH in Ald21 (class 1 mutant) was 85% lower than that of wild-type FALDH, while the specific activity of Ald24 (class 2 mutant) was 55% greater than that of wild-type FALDH. Ald21R, a dodecyl aldehyde-positive revertant able to grow on hexadecane, hexadecanol, and dodecyl aldehyde, exhibited a 100% increase in the specific activity of the NADP-dependent FALDH. The oxidation of [3H]hexadecane byAld21 yielded the accumulation of 61% more fatty aldehyde than the wild type, while Ald24 accumulated 27% more fatty aldehyde, 95% more fatty alcohol, and 65% more wax ester than the wild type. This study provides genetic and physiological evidence for the role of fatty aldehyde as an essential metabolic intermediate and NADP-dependent FALDH as a key enzyme in the dissimilation of hexadecane, hexadecanol, and dodecyl aldehyde in Acinetobactor sp. strain HO1-N. Images PMID:4066609

Colorimetric monitoring of solid-phase aldehydes using 2,4-dinitrophenylhydrazine.

PubMed

Shannon, Simon K; Barany, George

2004-01-01

A simple and rapid method to achieve colorimetric monitoring of resin-bound aldehydes, based on ambient temperature reaction with 2,4-dinitrophenylhydrazine (DNPH) in the presence of dilute acid, has been developed as an adjunct to solid-phase organic synthesis and combinatorial chemistry. By this test, the presence of aldehydes is indicated by a red to dark-orange appearance, within a minute. Alternatively, resins that are free of aldehydes or in which aldehyde functions have reacted completely retain their original color. The DNPH test was demonstrated for poly(ethylene glycol)-polystyrene (PEG-PS), aminomethyl polystyrene (AMP), cross-linked ethoxylate acrylate resin (CLEAR), and acryloylated O,O'-bis(2-aminopropyl)poly(ethylene glycol) (PEGA) supports and gave results visible to the naked eye at levels as low as 18 micromol of aldehyde per gram of resin.

Selective Radical Amination of Aldehydic C(sp2)–H Bonds with Fluoroaryl Azides via Co(II)-Based Metalloradical Catalysis: Synthesis of N-Fluoroaryl Amides from Aldehydes under Neutral and Nonoxidative Conditions

PubMed Central

Jin, Li-Mei; Lu, Hongjian; Cui, Yuan; Lizardi, Christopher L.; Arzua, Thiago N.; Wojtas, Lukasz; Cui, Xin

2014-01-01

The Co(II) complex of the D2h-symmetric amidoporphyrin 3,5-DitBu-IbuPhyrin, [Co(P1)], has proven to be an effective metalloradical catalyst for intermolecular amination of C(sp2)–H bonds of aldehydes with fluoroaryl azides. The [Co(P1)]-catalyzed process can employ aldehydes as the limiting reagents and operate under neutral and non-oxidative conditions, generating nitrogen gas as the only byproduct. The metalloradical aldehydic C–H amination is suitable for different combinations of aldehydes and fluoroaryl azides, producing the corresponding N-fluoroaryl amides in good to excellent yields. A series of mechanistic studies support a stepwise radical mechanism for the Co(II)-catalyzed intermolecular C–H amination. PMID:25071929

Selective Radical Amination of Aldehydic C(sp2)-H Bonds with Fluoroaryl Azides via Co(II)-Based Metalloradical Catalysis: Synthesis of N-Fluoroaryl Amides from Aldehydes under Neutral and Nonoxidative Conditions.

PubMed

Jin, Li-Mei; Lu, Hongjian; Cui, Yuan; Lizardi, Christopher L; Arzua, Thiago N; Wojtas, Lukasz; Cui, Xin; Zhang, X Peter

2014-06-01

The Co(II) complex of the D 2h -symmetric amidoporphyrin 3,5-Di t Bu-IbuPhyrin, [Co( P1 )], has proven to be an effective metalloradical catalyst for intermolecular amination of C(sp 2 )-H bonds of aldehydes with fluoroaryl azides. The [Co( P1 )]-catalyzed process can employ aldehydes as the limiting reagents and operate under neutral and non-oxidative conditions, generating nitrogen gas as the only byproduct. The metalloradical aldehydic C-H amination is suitable for different combinations of aldehydes and fluoroaryl azides, producing the corresponding N -fluoroaryl amides in good to excellent yields. A series of mechanistic studies support a stepwise radical mechanism for the Co(II)-catalyzed intermolecular C-H amination.

Respiratory Effects and Systemic Stress Response Following Acute Acrolein Inhalation in Rats.

EPA Science Inventory

Previous studies have demonstrated that exposure to the pulmonary irritant ozone causes myriad systemic metabolic and pulmonary effects attributed to sympathetic and hypothalamus-pituitary-adrenal (HPA) axis activation, which are exacerbated in metabolically impaired models. We...

Systemic Metabolic Impairment and Lung Injury Following Acrolein Inhalation

EPA Science Inventory

A single ozone exposure causes pulmonary injury and systemic metabolic alterations through neuronal and hypothalamus pituitary adrenal axis activation. Metabolically impaired Goto Kakizaki (GK) rats with non-obese type-2 diabetes are more sensitive to ozone induced changes than h...

Respiratory Effects and Systemic Stress Response Following Acute Acrolein Inhalation in Rats

EPA Science Inventory

Previous studies have demonstrated that exposure to ozone, a pulmonary irritant, causes myriad systemic metabolic and pulmonary effects that are attributed to neuronal and hypothalamus-pituitary-adrenal (HPA) axis activation, which are exacerbated in metabolically-impaired models...

40 CFR 63.2240 - What are the compliance options and operating requirements and how must I meet them?

Code of Federal Regulations, 2011 CFR

2011-07-01

... include acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde from your affected... obtained according to § 63.2262(b) through (d), (g), and (h), using the methods specified in Table 4 to...

40 CFR 63.2240 - What are the compliance options and operating requirements and how must I meet them?

Code of Federal Regulations, 2010 CFR

2010-07-01

... include acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde from your affected... obtained according to § 63.2262(b) through (d), (g), and (h), using the methods specified in Table 4 to...

Insight into Coenzyme A cofactor binding and the mechanism of acyl-transfer in an acylating aldehyde dehydrogenase from Clostridium phytofermentans

PubMed Central

Tuck, Laura R.; Altenbach, Kirsten; Ang, Thiau Fu; Crawshaw, Adam D.; Campopiano, Dominic J.; Clarke, David J.; Marles-Wright, Jon

2016-01-01

The breakdown of fucose and rhamnose released from plant cell walls by the cellulolytic soil bacterium Clostridium phytofermentans produces toxic aldehyde intermediates. To enable growth on these carbon sources, the pathway for the breakdown of fucose and rhamnose is encapsulated within a bacterial microcompartment (BMC). These proteinaceous organelles sequester the toxic aldehyde intermediates and allow the efficient action of acylating aldehyde dehydrogenase enzymes to produce an acyl-CoA that is ultimately used in substrate-level phosphorylation to produce ATP. Here we analyse the kinetics of the aldehyde dehydrogenase enzyme from the fucose/rhamnose utilisation BMC with different short-chain fatty aldehydes and show that it has activity against substrates with up to six carbon atoms, with optimal activity against propionaldehyde. We have also determined the X-ray crystal structure of this enzyme in complex with CoA and show that the adenine nucleotide of this cofactor is bound in a distinct pocket to the same group in NAD+. This work is the first report of the structure of CoA bound to an aldehyde dehydrogenase enzyme and our crystallographic model provides important insight into the differences within the active site that distinguish the acylating from non-acylating aldehyde dehydrogenase enzymes. PMID:26899032

Insight into Coenzyme A cofactor binding and the mechanism of acyl-transfer in an acylating aldehyde dehydrogenase from Clostridium phytofermentans.

PubMed

Tuck, Laura R; Altenbach, Kirsten; Ang, Thiau Fu; Crawshaw, Adam D; Campopiano, Dominic J; Clarke, David J; Marles-Wright, Jon

2016-02-22

The breakdown of fucose and rhamnose released from plant cell walls by the cellulolytic soil bacterium Clostridium phytofermentans produces toxic aldehyde intermediates. To enable growth on these carbon sources, the pathway for the breakdown of fucose and rhamnose is encapsulated within a bacterial microcompartment (BMC). These proteinaceous organelles sequester the toxic aldehyde intermediates and allow the efficient action of acylating aldehyde dehydrogenase enzymes to produce an acyl-CoA that is ultimately used in substrate-level phosphorylation to produce ATP. Here we analyse the kinetics of the aldehyde dehydrogenase enzyme from the fucose/rhamnose utilisation BMC with different short-chain fatty aldehydes and show that it has activity against substrates with up to six carbon atoms, with optimal activity against propionaldehyde. We have also determined the X-ray crystal structure of this enzyme in complex with CoA and show that the adenine nucleotide of this cofactor is bound in a distinct pocket to the same group in NAD(+). This work is the first report of the structure of CoA bound to an aldehyde dehydrogenase enzyme and our crystallographic model provides important insight into the differences within the active site that distinguish the acylating from non-acylating aldehyde dehydrogenase enzymes.

Control of aldehyde emissions in the diesel engines with alcoholic fuels.

PubMed

Krishna, M V S Murali; Varaprasad, C M; Reddy, C Venkata Ramana

2006-01-01

The major pollutants emitted from compression ignition (CI) engine with diesel as fuel are smoke and nitrogen oxides (NOx). When the diesel engine is run with alternate fuels, there is need to check alcohols (methanol or ethanol) and aldehydes also. Alcohols cannot be used directly in diesel engine and hence engine modification is essential as alcohols have low cetane number and high latent hear of vaporization. Hence, for use of alcohol in diesel engine, it needs hot combustion chamber, which is provided by low heat rejection (LHR) diesel engine with an air gap insulated piston with superni crown and air gap insulated liner with superni insert. In the present study, the pollution levels of aldehydes are reported with the use of methanol and ethanol as alternate fuels in LHR diesel engine with varying injection pressure, injection timings with different percentage of alcohol induction. The aldehydes (formaldehyde and acetaldehyde) in the exhaust were estimated by wet chemical technique with high performance liquid chromatograph (HPLC). Aldehyde emissions increased with an increase in alcohol induction. The LHR engine showed a decrease in aldehyde emissions when compared to conventional engine. However, the variation of injection pressure showed a marginal effect in reducing aldehydes, while advancing the injection timing reduced aldehyde emissions.

Fatty Aldehyde and Fatty Alcohol Metabolism: Review and Importance for Epidermal Structure and Function

PubMed Central

Rizzo, William B.

2014-01-01

Normal fatty aldehyde and alcohol metabolism is essential for epidermal differentiation and function. Long-chain aldehydes are produced by catabolism of several lipids including fatty alcohols, sphingolipids, ether glycerolipids, isoprenoid alcohols and certain aliphatic lipids that undergo α- or ω-oxidation. The fatty aldehyde generated by these pathways is chiefly metabolized to fatty acid by fatty aldehyde dehydrogenase (FALDH, alternately known as ALDH3A2), which also functions to oxidize fatty alcohols as a component of the fatty alcohol:NAD oxidoreductase (FAO) enzyme complex. Genetic deficiency of FALDH/FAO in patients with Sjögren-Larsson syndrome (SLS) results in accumulation of fatty aldehydes, fatty alcohols and related lipids (ether glycerolipids, wax esters) in cultured keratinocytes. These biochemical changes are associated with abnormalities in formation of lamellar bodies in the stratum granulosum and impaired delivery of their precursor membranes to the stratum corneum (SC). The defective extracellular SC membranes are responsible for a leaky epidermal water barrier and ichthyosis. Although lamellar bodies appear to be the pathogenic target for abnormal fatty aldehyde/alcohol metabolism in SLS, the precise biochemical mechanisms are yet to be elucidated. Nevertheless, studies in SLS highlight the critical importance of FALDH and normal fatty aldehyde/alcohol metabolism for epidermal function. PMID:24036493

Cellular fatty acids and aldehydes of oral Eubacterium.

PubMed

Itoh, U; Sato, M; Tsuchiya, H; Namikawa, I

1995-02-01

The cellular fatty acids and aldehydes of oral Eubacterium species were determined by gas chromatography-mass spectrometry. E. brachy and E. lentum contained mainly branched-chain fatty acids, whereas the others contained straight-chain acids. E. brachy, E. lentum, E. yurii ssp. yurii, E. yurii spp. margaretiae, E. limosum, E. plauti and E. aerofaciens also contained aldehydes with even carbon numbers. In addition to species-specific components, the compositional ratios of fatty acids and aldehydes characterized each individual species. The 10 species tested were divided into 5 groups by the principal component analysis. Cellular fatty acids and aldehydes would be chemical markers for interspecies differentiation of oral Eubacterium.

Molecular Structure and Reactivity in the Pyrolysis of Aldehydes

NASA Astrophysics Data System (ADS)

Sias, Eric; Cole, Sarah; Sowards, John; Warner, Brian; Wright, Emily; McCunn, Laura R.

2016-06-01

The effect of alkyl chain structure on pyrolysis mechanisms has been investigated in a series of aldehydes. Isovaleraldehyde, CH_3CH(CH_3)CH_2CHO, and pivaldehyde, (CH_3)_3CCHO, were subject to thermal decomposition in a resistively heated SiC tubular reactor at 800-1200 °C. Matrix-isolation FTIR spectroscopy was used to identify pyrolysis products. Carbon monoxide and isobutene were major products from each of the aldehydes, which is consistent with what is known from previous studies of unbranched alkyl-chain aldehydes. Other products observed include vinyl alcohol, propene, acetylene, and ethylene, revealing complexities to be considered in the pyrolysis of large, branched-chain aldehydes.

Domino-hydroformylation/aldol condensation catalysis: highly selective synthesis of α,β-unsaturated aldehydes from olefins.

PubMed

Fang, Xianjie; Jackstell, Ralf; Franke, Robert; Beller, Matthias

2014-10-06

A general and highly chemo-, regio-, and stereoselective synthesis of α,β-unsaturated aldehydes by a domino hydroformylation/aldol condensation reaction has been developed. A variety of olefins and aromatic aldehydes were efficiently converted into various substituted α,β-unsaturated aldehydes in good to excellent yields in the presence of a rhodium phosphine/acid-base catalyst system. In view of the easy availability of the substrates, the high atom-efficiency, the excellent selectivity, and the mild conditions, this method is expected to complement current methodologies for the preparation of α,β-unsaturated aldehydes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Proline-catalysed asymmetric amination of alpha,alpha-disubstituted aldehydes: synthesis of configurationally stable enantioenriched alpha-aminoaldehydes.

PubMed

Vogt, Henning; Vanderheiden, Sylvia; Bräse, Stefan

2003-10-07

Proline-catalysed amination of alpha,alpha-disubstituted racemic aldehydes with azodicarboxylates proceeds smoothly to give configurationally stable scalemic aldehydes and oxazolidinones in up to 86% ee.

Palladium-Catalyzed Anti-Markovnikov Oxidation of Allylic Amides to Protected β-Amino Aldehydes.

PubMed

Dong, Jia Jia; Harvey, Emma C; Fañanás-Mastral, Martín; Browne, Wesley R; Feringa, Ben L

2014-12-10

A general method for the preparation of N-protected β-amino aldehydes from allylic amines or linear allylic alcohols is described. Here the Pd(II)-catalyzed oxidation of N-protected allylic amines with benzoquinone is achieved in tBuOH under ambient conditions with excellent selectivity toward the anti-Markovnikov aldehyde products and full retention of configuration at the allylic carbon. The method shows a wide substrate scope and is tolerant of a range of protecting groups. Furthermore, β-amino aldehydes can be obtained directly from protected allylic alcohols via palladium-catalyzed autotandem reactions, and the application of this method to the synthesis of β-peptide aldehydes is described. From a mechanistic perspective, we demonstrate that tBuOH acts as a nucleophile in the reaction and that the initially formed tert-butyl ether undergoes spontaneous loss of isobutene to yield the aldehyde product. Furthermore, tBuOH can be used stoichiometrically, thereby broadening the solvent scope of the reaction. Primary and secondary alcohols do not undergo elimination, allowing the isolation of acetals, which subsequently can be hydrolyzed to their corresponding aldehyde products.

Chemo- and Diastereoselective N-Heterocyclic Carbene-Catalyzed Cross-Benzoin Reactions Using N-Boc-α-amino Aldehydes.

PubMed

Haghshenas, Pouyan; Gravel, Michel

2016-09-16

N-Boc-α-amino aldehydes are shown to be excellent partners in cross-benzoin reactions with aliphatic or heteroaromatic aldehydes. The chemoselectivity of the reaction and the facial selectivity on the amino aldehyde allow cross-benzoin products to be obtained in good yields and good diastereomeric ratios. The developed method is utilized as the key step in a concise total synthesis of d-arabino-phytosphingosine.

Tissue Repair and Regeneration Following Orthopedic and Craniofacial Trauma

DTIC Science & Technology

2012-07-01

than amines to aldehydes and ketones , and reaction of hydrazines with aldehydes results in the formation of a stable hydrazone bond. In that regard...their N-terminus that was oxidized with periodate to obtain a single aldehyde group at the same location, which can be used for the site-specific...specific immobiliza- tion on the HA surface. Specifically, both proteins were oxidized selectively to obtain an N-terminal aldehyde and immobilized on the

Resolution and partial characterization of two aldehyde reductases of mammalian liver.

PubMed

Tulsiani, D R; Touster

1977-04-25

Investigation of NADP-dependent aldehyde reductase activity in mouse liver led to the finding that two distinct reductases are separable by DE52 ion exchange chromatography. Aldehyde reductase I (AR I) appears in the effluent, while aldehyde reductase II (AR II) is eluted with a salt gradient. By several procedures AR II was purified over 1100-fold from liver supernatant fraction, but AR I could be pruified only 107-fold because of its instability. The two enzymes are different in regard to pH optimum, substrate specificity, response to inhibitors, and reactivity with antibody to AR II. While both enzymes utilize aromatic aldehydes well, only AR II ACTS ON D-glucuronate, indicating that it is the aldyhyde reductase recently reported to be identical to NADP-L-gulonate dehydrogenase. The presence of two NADP-linked aldehyde reductases in liver has apparently not heretofore been reported.

Spacecraft Maximum Allowable Concentrations (SMACs) for C3 to C8 Aliphatic Saturated Aldehydes

NASA Technical Reports Server (NTRS)

Langford, Shannon D.

2007-01-01

Spacecraft maximum allowable concentrations (SMACs) for C3 to C8, straight-chain, aliphatic aldehydes have been previously assessed and have been documented in volume 4 of Spacecraft Maximum Allowable Concentrations for Selected Airborne Contaminants (James, 2000). These aldehydes as well as associated physical properties are shown in Table 1. The C3 to C8 aliphatic aldehydes can enter the habitable compartments and contaminate breathing air of spacecraft by several routes including incomplete oxidation of alcohols in the Environmental Control and Life Support System (ECLSS) air revitalization subsystem, as a byproduct of human metabolism, through materials off-gassing, or during food preparation. These aldehydes have been detected in the atmosphere of manned space vehicles in the past. Analysis performed by NASA of crew cabin air samples from the Russian Mir Space Station revealed the presence of C3 to C8 aldehydes at concentrations peaking at approximately 0.1 mg/cu m.

Identification of stable cytotoxic factors in the gas phase extract of cigarette smoke and pharmacological characterization of their cytotoxicity.

PubMed

Noya, Yoichi; Seki, Koh-Ichi; Asano, Hiroshi; Mai, Yosuke; Horinouchi, Takahiro; Higashi, Tsunehito; Terada, Koji; Hatate, Chizuru; Hoshi, Akimasa; Nepal, Prabha; Horiguchi, Mika; Kuge, Yuji; Miwa, Soichi

2013-12-06

Smoking is a major risk factor for atherosclerotic vascular diseases, but the mechanism for its genesis is unknown. We have recently shown that the gas phase of cigarette smoke (nicotine- and tar-free cigarette smoke extract; CSE) likely to reach the systemic circulation contains stable substances which cause cytotoxicity like plasma membrane damage and cell death in cultured cells, and also that the plasma membrane damage is caused through sequential activation of protein kinase C (PKC) and NADPH oxidase (NOX) and the resulting generation of reactive oxygen species (PKC/NOX-dependent mechanism), whereas cell death is caused through PKC/NOX-dependent and -independent mechanisms. To identify these stable substances, the CSE was prepared by passing the main-stream smoke of 10 cigarettes through a Cambridge glass fiber filter, trapping of the smoke in a vessel cooled at -80°C, and subsequent dissolution in 10ml of water. The CSE was fractionated into nine fractions using reversed-phase HPLC, and each fraction was screened for cytotoxicity in cultured cells, using propidium iodide uptake assay for cell membrane damage and MTS [3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium] reduction assay for cell viability. The cytotoxicity was positive in two of the nine fractions (Fr2 and Fr5). After extraction of the active fractions into dichloromethane, GC/MS analysis identified 2-cyclopenten-1-one (CPO) in Fr5 but none in Fr2. After derivatization of the active fractions with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride, GC/MS analysis identified acrolein, acetone and propionaldehyde in Fr2, and methyl vinyl ketone (MVK) in Fr5. After 4-h incubation, authentic acrolein and MVK induced concentration-dependent cytotoxicity with EC50 values of 75.9±8.2 and 47.0±8.0μM (mean±SEM; n=3), respectively, whereas acetone, propionaldehyde and CPO were without effect. However, after 24-h incubation, CPO induced concentration-dependent cytotoxicity with an EC50 value of 264.0±16.9μM (n=3). The concentrations of acrolein, MVK and CPO in the CSE were 3368±334, 2429±123 and 392.9±31.8μM (n=4), respectively, which were higher than the cytotoxic concentrations. The cytotoxicity of acrolein and MVK consisted of plasma membrane damage and decreased cell viability: the plasma membrane damage was totally prevented by treatment with an inhibitor of PKC or NOX, whereas the decreased cell viability was only partially prevented by these inhibitors. The cytotoxicity of CPO consisted only of decreased cell viability, which was totally resistant to these inhibitors. These results show that acrolein and MVK are responsible for the acute cytotoxicity of the CSE through PKC/NOX-dependent and -independent mechanisms, whereas CPO is responsible for the delayed cytotoxicity of the CSE through a PKC/NOX-independent mechanism. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Acrolein Inhalation Alters Arterial Blood Gases and Triggers Carotid Body Mediated Cardiovascular Responses in Hypertensive Rats

EPA Science Inventory

Exposure to air pollution increases risk of cardiovascular morbidity and mortality, especially in individuals with underlying cardiopulmonary disease. While the mechanisms accounting for these effects are unclear, several epidemiological studies have reported decreases in oxygen ...

Modeling the protection afforded by burrows, cavities, and roosts during wildland surface fires

Treesearch

Anthony Bova; Matthew Dickinson

2009-01-01

Wildland surface fires produce many toxic and irritating compounds, such as formaldehyde and acrolein, and harmful gases such as carbon monoxide. Several factors influence the degree of protection offered by animal shelters against combustion products and heat.

Provisional Peer-Reviewed Toxicity Values for Acrolein

EPA Science Inventory

Provisional Peer-Reviewed Toxicity Values (PPRTV) assessments are developed for use by the Agency’s Office of Land and Emergency Management (OLEM) to support informed decisions in the Superfund program and at hazardous waste sites when a values is not available in the Integrated ...

Detoxification of aldehydes by histidine-containing dipeptides: from chemistry to clinical implications

PubMed Central

Xie, Zhengzhi; Baba, Shahid P.; Sweeney, Brooke R.; Barski, Oleg A.

2015-01-01

Aldehydes are generated by oxidized lipids and carbohydrates at increased levels under conditions of metabolic imbalance and oxidative stress during atherosclerosis, myocardial and cerebral ischemia, diabetes, neurodegenerative diseases and trauma. In most tissues, aldehydes are detoxified by oxidoreductases that catalyze the oxidation or the reduction of aldehydes or enzymatic and nonenzymatic conjugation with low molecular weight thiols and amines, such as glutathione and histidine dipeptides. Histidine dipeptides are present in micromolar to millimolar range in the tissues of vertebrates, where they are involved in a variety of physiological functions such as pH buffering, metal chelation, oxidant and aldehyde scavenging. Histidine dipeptides such as carnosine form Michael adducts with lipid-derived unsaturated aldehydes, and react with carbohydrate-derived oxo- and hydroxy- aldehydes forming products of unknown structure. Although these peptides react with electrophilic molecules at lower rate than glutathione, they can protect glutathione from modification by oxidant and they may be important for aldehyde quenching in glutathione-depleted cells or extracellular space where glutathione is scarce. Consistent with in vitro findings, treatment with carnosine has been shown to diminish ischemic injury, improve glucose control, ameliorate the development of complications in animal models of diabetes and obesity, promote wound healing and decrease atherosclerosis. The protective effects of carnosine have been linked to its anti-oxidant properties, it ability to promote glycolysis, detoxify reactive aldehydes and enhance histamine levels. Thus, treatment with carnosine and related histidine dipeptides may be a promising strategy for the prevention and treatment of diseases associated with high carbonyl load. PMID:23313711

The use of tomato aminoaldehyde dehydrogenase 1 for the detection of aldehydes in fruit distillates.

PubMed

Frömmel, Jan; Tarkowski, Petr; Kopečný, David; Šebela, Marek

2016-09-25

Plant NAD(+)-dependent aminoaldehyde dehydrogenases (AMADHs, EC 1.2.1.19) belong to the family 10 of aldehyde dehydrogenases. They participate in the metabolism of polyamines or osmoprotectants. The enzymes are characterized by their broad substrate specificity covering ω-aminoaldehydes, aliphatic and aromatic aldehydes as well as nitrogen-containing heterocyclic aldehydes. The isoenzyme 1 from tomato (Solanum lycopersicum; SlAMADH1) oxidizes aliphatic aldehydes very efficiently and converts also furfural, its derivatives or benzaldehyde, which are present at low concentrations in alcoholic distillates such as fruit brandy. In this work, SlAMADH1 was examined as a bioanalytical tool for their detection. These aldehydes arise from fermentation processes or thermal degradation of sugars and their presence is related to health complications after consumption including nausea, emesis, sweating, decrease in blood pressure, hangover headache, among others. Sixteen samples of slivovitz (plum brandy) from local producers in Moravia, Czech Republic, were analyzed for their aldehyde content using a spectrophotometric activity assay with SlAMADH1. In all cases, there were oxidative responses observed when monitoring NADH production in the enzymatic reaction. Aldehydes in the distillate samples were also subjected to a standard determination using reversed-phase HPLC with spectrophotometric and tandem mass spectrometric detection after a derivatization with 2,4-dinitrophenylhydrazine. Results obtained by both methods were found to correlate well for a majority of the analyzed samples. The possible applicability of SlAMADH1 for the evaluation of aldehyde content in food and beverages has now been demonstrated. Copyright © 2015 Elsevier B.V. All rights reserved.

Detoxification of aldehydes by histidine-containing dipeptides: from chemistry to clinical implications.

PubMed

Xie, Zhengzhi; Baba, Shahid P; Sweeney, Brooke R; Barski, Oleg A

2013-02-25

Aldehydes are generated by oxidized lipids and carbohydrates at increased levels under conditions of metabolic imbalance and oxidative stress during atherosclerosis, myocardial and cerebral ischemia, diabetes, neurodegenerative diseases and trauma. In most tissues, aldehydes are detoxified by oxidoreductases that catalyze the oxidation or the reduction of aldehydes or enzymatic and nonenzymatic conjugation with low molecular weight thiols and amines, such as glutathione and histidine dipeptides. Histidine dipeptides are present in micromolar to millimolar range in the tissues of vertebrates, where they are involved in a variety of physiological functions such as pH buffering, metal chelation, oxidant and aldehyde scavenging. Histidine dipeptides such as carnosine form Michael adducts with lipid-derived unsaturated aldehydes, and react with carbohydrate-derived oxo- and hydroxy-aldehydes forming products of unknown structure. Although these peptides react with electrophilic molecules at lower rate than glutathione, they can protect glutathione from modification by oxidant and they may be important for aldehyde quenching in glutathione-depleted cells or extracellular space where glutathione is scarce. Consistent with in vitro findings, treatment with carnosine has been shown to diminish ischemic injury, improve glucose control, ameliorate the development of complications in animal models of diabetes and obesity, promote wound healing and decrease atherosclerosis. The protective effects of carnosine have been linked to its anti-oxidant properties, its ability to promote glycolysis, detoxify reactive aldehydes and enhance histamine levels. Thus, treatment with carnosine and related histidine dipeptides may be a promising strategy for the prevention and treatment of diseases associated with high carbonyl load. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Substrate specificity and catalytic efficiency of aldo-keto reductases with phospholipid aldehydes

PubMed Central

Spite, Matthew; Baba, Shahid P.; Ahmed, Yonis; Barski, Oleg A.; Nijhawan, Kanchan; Petrash, J. Mark; Bhatnagar, Aruni; Srivastava, Sanjay

2007-01-01

Phospholipid oxidation generates several bioactive aldehydes that remain esterified to the glycerol backbone (‘core’ aldehydes). These aldehydes induce endothelial cells to produce monocyte chemotactic factors and enhance monocyte–endothelium adhesion. They also serve as ligands of scavenger receptors for the uptake of oxidized lipoproteins or apoptotic cells. The biochemical pathways involved in phospholipid aldehyde metabolism, however, remain largely unknown. In the present study, we have examined the efficacy of the three mammalian AKR (aldo-keto reductase) families in catalysing the reduction of phospholipid aldehydes. The model phospholipid aldehyde POVPC [1-palmitoyl-2-(5-oxovaleroyl)-sn-glycero-3-phosphocholine] was efficiently reduced by members of the AKR1, but not by the AKR6 or the ARK7 family. In the AKR1 family, POVPC reductase activity was limited to AKR1A and B. No significant activity was observed with AKR1C enzymes. Among the active proteins, human AR (aldose reductase) (AKR1B1) showed the highest catalytic activity. The catalytic efficiency of human small intestinal AR (AKR1B10) was comparable with the murine AKR1B proteins 1B3 and 1B8. Among the murine proteins AKR1A4 and AKR1B7 showed appreciably lower catalytic activity as compared with 1B3 and 1B8. The human AKRs, 1B1 and 1B10, and the murine proteins, 1B3 and 1B8, also reduced C-7 and C-9 sn-2 aldehydes as well as POVPE [1-palmitoyl-2-(5-oxovaleroyl)-sn-glycero-3-phosphoethanolamine]. AKR1A4, B1, B7 and B8 catalysed the reduction of aldehydes generated in oxidized C16:0-20:4 phosphatidylcholine with acyl, plasmenyl or alkyl linkage at the sn-1 position or C16:0-20:4 phosphatidylglycerol or phosphatidic acid. AKR1B1 displayed the highest activity with phosphatidic acids; AKR1A4 was more efficient with long-chain aldehydes such as 5-hydroxy-8-oxo-6-octenoyl derivatives, whereas AKR1B8 preferred phosphatidylglycerol. These results suggest that proteins of the AKR1A and B families are efficient phospholipid aldehyde reductases, with non-overlapping substrate specificity, and may be involved in tissue-specific metabolism of endogenous or dietary phospholipid aldehydes. PMID:17381426

Nickel-Catalyzed, Carbonyl-Ene-Type Reactions: Selective for Alpha Olefins and More Efficient with Electron-Rich Aldehydes

PubMed Central

Ho, Chun-Yu; Ng, Sze-Sze; Jamison, Timothy F.

2011-01-01

Described are several classes of unusual or unprecedented carbonyl-ene-type reactions, including those between alpha olefins and aromatic aldehydes. Catalyzed by nickel, these processes complement existing Lewis acid-catalyzed methods in several respects. Not only are monosubstituted alkenes, aromatic aldehydes, and tert-alkyl aldehydes effective substrates, but monosubstituted olefins also react faster than those that are more substituted, and large or electron-rich aldehydes are more effective than small or electron-poor ones. Conceptually, in the presence of a nickel-phosphine catalyst, the combination of off-the-shelf alkenes, silyl triflates, and triethylamine functions as a replacement for an allylmetal reagent. PMID:16620106

Community air monitoring for pesticides. Part 3: using health-based screening levels to evaluate results collected for a year.

PubMed

Wofford, Pamela; Segawa, Randy; Schreider, Jay; Federighi, Veda; Neal, Rosemary; Brattesani, Madeline

2014-03-01

The CA Department of Pesticide Regulation (CDPR) and the CA Air Resources Board monitored 40 pesticides, including five degradation products, in Parlier, CA, to determine if its residents were exposed to any of these pesticides and, if so, in what amounts. They included 1,3-dichloropropene, acrolein, arsenic, azinphos-methyl, carbon disulfide, chlorpyrifos and its degradation product, chlorthalonil, copper, cypermethrin, diazinon and its degradation product, dichlorvos, dicofol, dimethoate and its degradation product, diuron, endosulfan and its degradation product, S-ethyl dipropylcarbamothioate (EPTC), formaldehyde, malathion and its degradation product, methyl isothiocyanate (MITC), methyl bromide, metolachlor, molinate, norflurazon, oryzalin, oxyfluorfen, permethrin, phosmet, propanil, propargite, simazine, SSS-tributylphosphorotrithioate, sulfur, thiobencarb, trifluralin, and xylene. Monitoring was conducted 3 days per week for a year. Twenty-three pesticides and degradation products were detected. Acrolein, arsenic, carbon disulfide, chlorpyrifos, copper, formaldehyde, methyl bromide, MITC, and sulfur were detected in more than half the samples. Since no regulatory ambient air standards exist for these pesticides, CDPR developed advisory, health-based non-cancer screening levels (SLs) to assess acute, subchronic, and chronic exposures. For carcinogenic pesticides, CDPR assessed risk using cancer potency values. Amongst non-carcinogenic agricultural use pesticides, only diazinon exceeded its SL. For carcinogens, 1,3-dichloropropene concentrations exceeded its cancer potency value. Based on these findings, CDPR has undertaken a more comprehensive evaluation of 1,3-dichloropropene, diazinon, and the closely related chlorpyrifos that was frequently detected. Four chemicals-acrolein, arsenic, carbon disulfide, and formaldehyde-sometimes used as pesticides were detected, although no pesticidal use was reported in the area during this study. Their presence was most likely due to vehicular or industrial emissions.

A Real-Time Fast-Flow Tube Study of VOC and Particulate Emissions from Electronic, Potentially Reduced-Harm, Conventional, and Reference Cigarettes

PubMed Central

Blair, Sandra L.; Epstein, Scott A.; Nizkorodov, Sergey A.; Staimer, Norbert

2015-01-01

Tobacco-free electronic cigarettes (e-cigarettes), which are currently not regulated by the FDA, have become widespread as a “safe” form of smoking. One approach to evaluate the potential toxicity of e-cigarettes and other types of potentially “reduced-harm” cigarettes is to compare their emissions of volatile organic compounds (VOCs), including reactive organic electrophillic compounds such as acrolein, and particulate matter to those of conventional and reference cigarettes. Our newly designed fast-flow tube system enabled us to analyze VOC composition and particle number concentration in real-time by promptly diluting puffs of mainstream smoke obtained from different brands of combustion cigarettes and e-cigarettes. A proton transfer reaction time-of-flight mass spectrometer (PTRMS) was used to analyze real-time cigarette VOC emissions with a 1 s time resolution. Particles were detected with a condensation particle counter (CPC). This technique offers real-time analysis of VOCs and particles in each puff without sample aging and does not require any sample pretreatment or extra handling. Several important determining factors in VOC and particle concentration were investigated: (1) puff frequency; (2) puff number; (3) tar content; (4) filter type. Results indicate that electronic cigarettes are not free from acrolein and acetaldehyde emissions and produce comparable particle number concentrations to those of combustion cigarettes, more specifically to the 1R5F reference cigarette. Unlike conventional cigarettes, which emit different amounts of particles and VOCs each puff, there was no significant puff dependence in the e-cigarette emissions. Charcoal filter cigarettes did not fully prevent the emission of acrolein and other VOCs. PMID:26726281

Children’s Exposure to Secondhand and Thirdhand Smoke Carcinogens and Toxicants in Homes of Hookah Smokers

PubMed Central

Daffa, Reem M.; Liles, Sandy; Jackson, Sheila R.; Kassem, Noura O.; Younis, Maram A.; Mehta, Setoo; Chen, Menglan; Jacob, Peyton; Carmella, Steve G.; Chatfield, Dale A.; Benowitz, Neal L.; Matt, Georg E.; Hecht, Stephen S.; Hovell, Melbourne F.

2014-01-01

Introduction: We examined homes of hookah-only smokers and nonsmokers for levels of indoor air nicotine (a marker of secondhand smoke) and indoor surface nicotine (a marker of thirdhand smoke), child uptake of nicotine, the carcinogen 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), and the toxicant acrolein by analyzing their corresponding metabolites cotinine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) and NNAL-glucuronides (total NNAL) and 3-hydroxypropylmercapturic acid. Methods: Data were collected at 3 home visits during a 7-day study period from a convenience sample of 24 households with a child 5 years or younger. Three child urine samples and 2 air and surface samples from the living room and the child bedroom were taken in homes of nonsmokers (n = 5) and hookah-only smokers (n = 19) comprised of daily hookah smokers (n = 8) and weekly/monthly hookah smokers (n = 11). Results: Nicotine levels in indoor air and on surfaces in the child bedrooms in homes of daily hookah smokers were significantly higher than in homes of nonsmokers. Uptake of nicotine, NNK, and acrolein in children living in daily hookah smoker homes was significantly higher than in children living in nonsmoker homes. Uptake of nicotine and NNK in children living in weekly/monthly hookah smoker homes was significantly higher than in children living in nonsmoker homes. Conclusions: Our data provide the first evidence for uptake of nicotine, the tobacco-specific lung carcinogen NNK, and the ciliatoxic and cardiotoxic agent acrolein in children living in homes of hookah smokers. Our findings suggest that daily and occasional hookah use in homes present a serious, emerging threat to children’s long-term health. PMID:24590387

Synthesis and Characterization of Platinum-Ruthenium-Tin Catalysts

NASA Astrophysics Data System (ADS)

Uffalussy, Karen

Magnesia-supported trimetallic Pt-Ru-Sn catalysts prepared through a cluster and a conventional synthetic route have been investigated in terms of their structural properties and their catalytic activity for the hydrogenation of citral and crotonaldehyde. FTIR results indicate that the majority of the stabilizing ligands remain attached to the PtRu5(μ-SnPh 2)(C)(CO)15 cluster used following impregnation onto the MgO support. Under H2 reduction conditions, partial and full ligand removal are both observed at 473 and 573 K, respectively. HRSTEM analysis shows that cluster-derived samples exhibit significantly smaller average metal particle sizes, as well as narrower particle size distributions than the corresponding conventionally prepared ones. EDX measurements show that in the cluster-derived catalysts, the majority of the metal particles present are trimetallic in nature, with metal compositions similar to those of the original cluster. In contrast, the conventionally prepared materials contain mostly bimetallic and monometallic particles with variable compositions. XPS was used to determine how the variation in method of Sn addition to bimetallic Pt-Ru affects the electronic state for the trimetallic Pt-Ru-Sn/MgO system prepared by impregnation using multimetallic clusters, metal-salts, and the combination of both precursor types. Results show that the PtRu5Sn/MgO material has a significantly higher percentage of Sn0 in comparison to Pt-Ru-Sn/MgO and PtRu5-Sn/MgO, and a corresponding shift in both Pt and Ru peaks can be correlated to this relative change in Sn oxidation state. The formation of smaller metal particles and electronic modification of Pt and Ru by Sn in the cluster-derived catalysts and the presence of the three metals in these particles in close proximity result in higher activity and selectivity to the unsaturated alcohols for the hydrogenation of both citral and crotonaldehyde.

DIPPR Project 871 For 1995 - Thermodynamic Properties and Ideal-Gas Enthalpies of Formation for Methyl Benzoate, Ethyl Benzoate, (R)-(+)-Limonene, Tert-Amyl Methyl Ether, Trans-Crotonaldehyde, and

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steele, W.V.

2002-07-01

Ideal-gas enthalpies of formation of methyl benzoate, ethyl benzoate, (R)-(+)-limonene, tert-amyl methyl ether, trans-crotonaldehyde, and diethylene glycol are reported. The standard energy of combustion and hence standard enthalpy of formation of each compound in the liquid phase has been measured using an oxygen rotating-bomb calorimeter without rotation. Vapor pressures were measured to a pressure limit of 270 kPa or the lower decomposition point for each of the six compounds using a twin ebulliometric apparatus. Liquid-phase densities along the saturation line were measured for each compound over a range of temperature (ambient to a maximum of 548 K). A differential scanningmore » calorimeter was used to measure two-phase (liquid + vapor) heat capacities for each compound in the temperature region ambient to the critical temperature or lower decomposition point. For methyl benzoate and tert-amyl methyl ether, critical temperatures and critical densities were determined from the DSC results and corresponding critical pressures derived from the fitting procedures. Fitting procedures were used to derive critical temperatures, critical pressures, and critical densities for each of the remaining compounds. The results of the measurements were combined to derive a series of thermophysical properties including critical temperature, critical density, critical pressure, acentric factor, enthalpies of vaporization (restricted to within {+-}50 K of the temperature region of the experimentally determined vapor pressures), and heat capacities along the saturation line. Wagner-type vapor-pressure equations were derived for each compound. All measured and derived values were compared with those obtained in a search of the literature. Recommended critical parameters are listed for each of the compounds studied. Group-additivity parameters, useful in the application of the Benson gas-phase group-contribution correlations, were derived.« less

Pathway and Surface Mechanism Studies of 1,3-butadiene Selective Oxidation Over Vanadium-Molybdenum-Oxygen Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schroeder, William David

2001-01-01

The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m 2/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO 3/(MoO 3 + V 2O 5). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V +4 and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of watermore » to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The catalytic effects of water addition were related to competitive adsorption with various V 2O 5-based surface sites, including the vanadyl V=O, corner sharing V-O-V and edge sharing V-O oxygen. Higher levels of water addition were proposed to impose acidic character by dissociative adsorption. In addition, a novel combinatorial synthesis technique for VMoO was used to investigate the phase transitions of V 2O 5, solid solutions of Mo in V 2O 5, V 9Mo 6O 40, and other reduced VMoO compounds, characterized by laser Raman spectroscopy. The natural composition gradient imposed by the sputter deposition apparatus was used to create VMoO arrays containing 225 samples ranging from 7.0-42 mol% MoO 3/(V 2O 5 + MoO 3), determined by EDS analysis.« less

Process for producing furan from furfural aldehyde

DOEpatents

Diebold, James P.; Evans, Robert J.

1988-01-01

A process of producing furan and derivatives thereof is disclosed. The process includes generating furfural aldehyde vapors and then passing those vapors over a zeolite catalyst at a temperature and for a residence time effective to decarbonylate the furfural aldehydes to form furans and derivatives thereof. The resultant furan vapors and derivatives are then separated. In a preferred form, the furfural aldehyde vapors are generated during the process of converting biomass materials to liquid and gaseous fuels.

Process for producing furan from furfural aldehyde

DOEpatents

Diebold, J.P.; Evans, R.J.

1987-04-06

A process of producing furan and derivatives thereof as disclosed. The process includes generating furfural aldehyde vapors and then passing those vapors over a zeolite catalyst at a temperature and for a residence time effective to decarbonylate the furfural aldehydes to form furans and derivatives thereof. The resultant furan vapors and derivatives are then separated. In a preferred form, the furfural aldehyde vapors are generated during the process of converting biomass materials to liquid and gaseous fuels.

Microsphere coated substrate containing reactive aldehyde groups

NASA Technical Reports Server (NTRS)

Yen, Richard C. K. (Inventor); Rembaum, Alan (Inventor)

1984-01-01

A synthetic organic resin is coated with a continuous layer of contiguous, tangential, individual microspheres having a uniform diameter preferably between 100 Angstroms and 2000 Angstroms. The microspheres are an addition polymerized polymer of an unsaturated aldehyde containing 4 to 20 carbon atoms and are covalently bonded to the substrate by means of high energy radiation grafting. The microspheres contain reactive aldehyde groups and can form conjugates with proteins such as enzymes or other aldehyde reactive materials.

Different specificities of two aldehyde dehydrogenases from Saccharomyces cerevisiae var. boulardii.

PubMed

Datta, Suprama; Annapure, Uday S; Timson, David J

2017-04-30

Aldehyde dehydrogenases play crucial roles in the detoxification of exogenous and endogenous aldehydes by catalysing their oxidation to carboxylic acid counterparts. The present study reports characterization of two such isoenzymes from the yeast Saccharomyces cerevisiae var. boulardii (NCYC 3264), one mitochondrial (Ald4p) and one cytosolic (Ald6p). Both Ald4p and Ald6p were oligomeric in solution and demonstrated positive kinetic cooperativity towards aldehyde substrates. Wild-type Ald6p showed activity only with aliphatic aldehydes. Ald4p, on the contrary, showed activity with benzaldehyde along with a limited range of aliphatic aldehydes. Inspection of modelled structure of Ald6p revealed that a bulky amino acid residue (Met 177 , compared with the equivalent residue Leu 196 in Ald4p) might cause steric hindrance of cyclic substrates. Therefore, we hypothesized that specificities of the two isoenzymes towards aldehyde substrates were partly driven by steric hindrance in the active site. A variant of wild-type Ald6p with the Met 177 residue replaced by a valine was also characterized to address to the hypothesis. It showed an increased specificity range and a gain of activity towards cyclohexanecarboxaldehyde. It also demonstrated an increased thermal stability when compared with both the wild-types. These data suggest that steric bulk in the active site of yeast aldehyde dehydrogenases is partially responsible for controlling specificity. © 2017 The Author(s).

Anti-Inflammatory Activities of Cinnamomum cassia Constituents In Vitro and In Vivo

PubMed Central

Liao, Jung-Chun; Deng, Jeng-Shyan; Chiu, Chuan-Sung; Hou, Wen-Chi; Huang, Shyh-Shyun; Shie, Pei-Hsin; Huang, Guang-Jhong

2012-01-01

We have investigated the anti-inflammatory effects of Cinnamomum cassia constituents (cinnamic aldehyde, cinnamic alcohol, cinnamic acid, and coumarin) using lipopolysaccharide (LPS)-stimulated mouse macrophage (RAW264.7) and carrageenan (Carr)-induced mouse paw edema model. When RAW264.7 macrophages were treated with cinnamic aldehyde together with LPS, a significant concentration-dependent inhibition of nitric oxide (NO), tumor necrosis factor (TNF-α), and prostaglandin E2 (PGE2) levels productions were detected. Western blotting revealed that cinnamic aldehyde blocked protein expression of inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), nuclear transcription factor kappa B (NF-κB), and IκBα, significantly. In the anti-inflammatory test, cinnamic aldehyde decreased the paw edema after Carr administration, and increased the activities of catalase (CAT), superoxide dismutase (SOD), and glutathione peroxidase (GPx) in the paw tissue. We also demonstrated cinnamic aldehyde attenuated the malondialdehyde (MDA) level and myeloperoxidase (MPO) activity in the edema paw after Carr injection. Cinnamic aldehyde decreased the NO, TNF-α, and PGE2 levels on the serum level after Carr injection. Western blotting revealed that cinnamic aldehyde decreased Carr-induced iNOS, COX-2, and NF-κB expressions in the edema paw. These findings demonstrated that cinnamic aldehyde has excellent anti-inflammatory activities and thus has great potential to be used as a source for natural health products. PMID:22536283

Airborne aldehydes in cabin-air of commercial aircraft: Measurement by HPLC with UV absorbance detection of 2,4-dinitrophenylhydrazones.

PubMed

Rosenberger, Wolfgang; Beckmann, Bibiana; Wrbitzky, Renate

2016-04-15

This paper presents the strategy and results of in-flight measurements of airborne aldehydes during normal operation and reported "smell events" on commercial aircraft. The aldehyde-measurement is a part of a large-scale study on cabin-air quality. The aims of this study were to describe cabin-air quality in general and to detect chemical abnormalities during the so-called "smell-events". Adsorption and derivatization of airborne aldehydes on 2,4-dinitrophenylhydrazine coated silica gel (DNPH-cartridge) was applied using tailor-made sampling kits. Samples were collected with battery supplied personal air sampling pumps during different flight phases. Furthermore, the influence of ozone was investigated by simultaneous sampling with and without ozone absorption unit (ozone converter) assembled to the DNPH-cartridges and found to be negligible. The method was validated for 14 aldehydes and found to be precise (RSD, 5.5-10.6%) and accurate (recovery, 98-103 %), with LOD levels being 0.3-0.6 μg/m(3). According to occupational exposure limits (OEL) or indoor air guidelines no unusual or noticeable aldehyde pollution was observed. In total, 353 aldehyde samples were taken from two types of aircraft. Formaldehyde (overall average 5.7 μg/m(3), overall median 4.9 μg/m(3), range 0.4-44 μg/m(3)), acetaldehyde (overall average 6.5 μg/m(3), overall median 4.6, range 0.3-90 μg/m(3)) and mostly very low concentrations of other aldehydes were measured on 108 flights. Simultaneous adsorption and derivatization of airborne aldehydes on DNPH-cartridges to the Schiff bases and their HPLC analysis with UV absorbance detection is a useful method to measure aldehydes in cabin-air of commercial aircraft. Copyright © 2015 Elsevier B.V. All rights reserved.

Stable isotope labeling-solid phase extraction-mass spectrometry analysis for profiling of thiols and aldehydes in beer.

PubMed

Zheng, Shu-Jian; Wang, Ya-Lan; Liu, Ping; Zhang, Zheng; Yu, Lei; Yuan, Bi-Feng; Feng, Yu-Qi

2017-12-15

In this study, we developed a strategy for profiling of thiols and aldehydes in beer samples by stable isotope labeling-solid phase extraction-liquid chromatography-double precursor ion scan/double neutral loss scan-mass spectrometry analysis (SIL-SPE-LC-DPIS/DNLS-MS). A pair of isotope reagents (ω-bromoacetonylquinolinium bromide, BQB; ω-bromoacetonylquinolinium-d 7 bromide, BQB-d 7 ) were used to label thiols; while for the aldehydes, a pair of isotope reagents (4-(2-(trimethylammonio) ethoxy) benzenaminium halide, 4-APC; 4-(2-(trimethylammonio) ethoxy) benzenaminium halide-d 4 , 4-APC-d 4 ) were used. The labeled thiols and aldehydes were extracted and purified with solid-phase extraction, respectively, followed by LC-MS analysis. Using the proposed SIL-SPE-LC-DPIS/DNLS-MS methods, 76 thiol and 25 aldehyde candidates were found in beer. Furthermore, we established SIL-SPE-LC-MRM-MS methods for the relative quantitation of thiols and aldehydes in different beer samples. The results showed that the contents of thiols and aldehydes are closely related to the brands and origins of beers. Copyright © 2017 Elsevier Ltd. All rights reserved.

40 CFR 63.2262 - How do I conduct performance tests and establish operating requirements?

Code of Federal Regulations, 2011 CFR

2011-07-01

... or documentation of inlet methanol or formaldehyde concentration is required) and outlet of the... HAP, formaldehyde, methanol, or total hydrocarbon (THC) emission rates. (2) When showing compliance... acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde), THC, formaldehyde, or methanol in...

40 CFR 63.2262 - How do I conduct performance tests and establish operating requirements?

Code of Federal Regulations, 2010 CFR

2010-07-01

... or documentation of inlet methanol or formaldehyde concentration is required) and outlet of the... HAP, formaldehyde, methanol, or total hydrocarbon (THC) emission rates. (2) When showing compliance... acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde), THC, formaldehyde, or methanol in...

Early life persistent vitamin D deficiency exacerbates arrhythmias and autonomic imbalance following acrolein exposure in mice.

EPA Science Inventory

Epidemiological and animal data have conclusively linked adverse cardiovascular outcomes to air pollution exposure. As such, cardiovascular function is maintained by adequate levels of certain essential micronutrients like vitamin D. Unfortunately, vitamin D deficiency (VDD) has ...

TRPA1 mediates changes in heart rate variability and cardiac mechanical function in mice exposed to acrolein

EPA Science Inventory

Short-term exposure to ambient air pollution is linked with adverse cardiovascular effects. While previous research focused primarily on particulate matter-induced responses, gaseous air pollutants also contribute to cause short-term cardiovascular effects. Mechanisms underlying ...

The effects of drugs, other foreign compounds, and cigarette smoke on the synthesis of protein by lung slices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hellstern, K.; Curtis, C.G.; Powell, G.M.

1990-04-01

The incorporation of {sup 14}C-leucine into rabbit lung slices was monitored in the absence and presence of selected drugs and chemicals relevant to the perturbation of lung function and the development of lung disease. Known inhibitors of protein synthesis (cycloheximide and ricin) inhibited the incorporation of {sup 14}C-leucine. Marked inhibition was also recorded with the lung toxins paraquat and 4-ipomeanol. By contrast, orciprenaline, salbutamol, and terbutaline were without effect although some response was recorded with isoprenaline. The filtered gas phase of cigarette smoke and acrolein, one of its components, were inhibitory but protection was afforded by N-acetylcysteine. It is suggestedmore » that the inhibitory effects of cigarette smoke may be due to its acrolein content. It is further suggested that the use of lung slices and measurements of {sup 14}C-leucine incorporation provide valuable means for monitoring potential pulmonary toxins.« less

High-resolution synchrotron infrared spectroscopy of acrolein: The vibrational levels between 850 and 1020 cm-1

NASA Astrophysics Data System (ADS)

McKellar, A. R. W.; Billinghurst, B. E.; Xu, Li-Hong; Lees, R. M.

2015-11-01

Using spectra obtained at the Canadian Light Source synchrotron radiation facility, a previously unobserved out-of-plane vibration of trans-acrolein (propenal) is reliably assigned for the first time. Its origin is at 1002.01 cm-1, which is about 20 cm-1 higher than usually quoted in the past. This mode is thus labelled as v14, leaving the label v15 for the known vibration at 992.66 cm-1. Weak combination bands 171182 ← 182, 171131 ← 131, 121182 ← 181, and 171182 ← 181 are studied for the first time, and assignments in the known v11, v16, and v15 fundamental bands are also extended. The seven excited vibrations involved in these bands are analyzed, together with five more unobserved vibrations in the same region (850-1020 cm-1), in a large 12-state simultaneous fit which accounts for most of the many observed perturbations in the spectra.

Diastereoselective oxidative α-amination of aliphatic aldehydes catalyzed by iodine: synthesis of syn-γ-hydroxy-α-amino acetals.

PubMed

Zhang, Yun-Xiao; Zhang, An-Qi; Tian, Jie-Sheng; Loh, Teck-Peng

2013-12-28

Aldehydes can react with secondary amines to give α-amino acetals via the α-amination of aliphatic aldehydes catalyzed by iodine. The presence of an asymmetric hydroxylated center at the γ-position of the aldehyde was found to induce the stereoselective amino group. This method represents a stereoselective α-amination of γ-hydroxyaldehydes for the synthesis of syn-γ-hydroxy-α-amino acetals in good yields and reasonable diastereoselectivities under very mild conditions.

Simple one-pot conversion of aldehydes and ketones to enals.

PubMed

Valenta, Petr; Drucker, Natalie A; Bode, Jeffrey W; Walsh, Patrick J

2009-05-21

A simple and efficient method to convert aldehydes into alpha,beta-unsaturated aldehydes with a two-carbon homologation is presented. Hydroboration of ethoxy acetylene with BH(3).SMe(2) generates tris(ethoxyvinyl) borane. Transmetalation with diethylzinc, addition to aldehydes or ketones, and acidic workup affords enals. When the addition is quenched with anilinium hydrochloride, 1,2-dithioglycol, or acetic anhydride, the unsaturated imine, dithiolane, or 1,1-diacetate is isolated in high yield. These transformations can be performed in a one-pot procedure.

The Structural Insulated Panel SIP Hut: Preliminary Evaluation of Energy Efficiency and Indoor Air Quality

DTIC Science & Technology

2015-08-19

laboratory analysis using EPA TO-15, and collection of gas samples in sorbent tubes for later analysis of aldehydes using NIOSH Method 2016. Total VOCs...measurement can be a general qualitative indicator of IAQ problems; formaldehyde and other aldehydes are common organic gases emitted from OSB; and...table in the middle of the hut. 5.1.2.3 Formaldehyde and other aldehydes Aldehydes were measured using both Dräger-tubes and by NIOSH Method 2016. The

Ni-Catalyzed Dehydrogenative Cross-Coupling: Direct Transformation of Aldehydes to Esters and Amides

PubMed Central

Whittaker, Aaron M.; Dong, Vy M.

2015-01-01

By exploring a new mode of Ni-catalyzed cross-coupling, we have developed a protocol to transform both aromatic and aliphatic aldehydes into either esters or amides directly. The success of this oxidative coupling depends on the appropriate choice of catalyst and organic oxidant, including the use of either α,α,α-trifluoroacetophenone or excess aldehyde. We present mechanistic data that supports a catalytic cycle involving oxidative addition into the aldehyde C–H bond. PMID:25424967

Formation of high-molecular-weight compounds via the heterogeneous reactions of gaseous C8-C10 n-aldehydes in the presence of atmospheric aerosol components

NASA Astrophysics Data System (ADS)

Han, Yuemei; Kawamura, Kimitaka; Chen, Qingcai; Mochida, Michihiro

2016-02-01

A laboratory study on the heterogeneous reactions of straight-chain aldehydes was performed by exposing n-octanal, nonanal, and decanal vapors to ambient aerosol particles. The aerosol and blank filters were extracted using methanol. The extracts were nebulized and the resulting compositions were examined using a high-resolution time-of-flight aerosol mass spectrometer. The mass spectral analysis showed that the exposures of the aldehydes to aerosol samples increased the peak intensities in the high mass range. The peaks in the mass spectra of the aerosol samples after exposure to different aldehydes were characterized by a homologous series of peak shifts due to the addition of multiple CH2 units. This result is explained by the formation of high-molecular-weight (HMW) compounds that contain single or multiple aldehyde moieties. The HMW fragment peaks for the blank filters exposed to n-aldehydes were relatively weak, indicating an important contribution from the ambient aerosol components to the formation of the HMW compounds. Among the factors affecting the overall interaction of aldehydes with atmospheric aerosol components, gas phase diffusion possibly limited the reactions under the studied conditions; therefore, their occurrence to a similar degree in the atmosphere is not ruled out, at least for the reactions involving n-nonanal and decanal. The major formation pathways for the observed HMW products may be the self-reactions of n-aldehydes mediated by atmospheric aerosol components and the reactions of n-aldehydes with organic aerosol components. The observed formation of HMW compounds encourages further investigations into their effects on the aerosol properties as well as the organic aerosol mass in the atmosphere.

A dual substrate kinetic model for cytochrome P450BM3-F87G catalysis: simultaneous binding of long chain aldehydes and 4-fluorophenol.

PubMed

Ledford, Chelsea; McMahon, Monica; Whitesell, Ashley; Khan, Ghalib; Kandagatla, Suneel K; Hurst, Dow P; Reggio, Patricia H; Raner, Gregory M

2017-02-01

To develop a model for binding and catalysis associated with the stimulation of 4-fluorophenol (4-FP) oxidation in the presence of long chain aldehydes by the enzymatic catalyst, cytochrome P450 BM3 -F87G. A variation of the Michaeli-Menten kinetic model was employed to describe interactions at the active site of the enzyme, along with computer aided modeling approaches. In addition to the hydroquinone product arising from de-fluorination of 4-FP, a second product (p-fluorocatechol) was also observed and, like the hydroquinone, its rate of formation increased in the presence of the aldehyde. When only aldehyde was present with the enzyme, BM3-F87G catalyzed its oxidation to the corresponding carboxylic acid; however, this activity was inhibited when 4-FP was added to the reaction. A 3D computer model of the active site containing both aldehyde and 4-FP was generated, guided by these kinetic observations. Finally, partitioning between the two phenolic products was examined with an emphasis on the conditions directing the initial epoxidation at either the 2,3- or 3,4-positions on the substrate. Temperature, reaction time, substrate concentration, and the structure of the aldehyde had no substantial effect on the overall product ratios, however the NADPH coupling efficiency decreased when unsaturated aldehydes were included, or when the temperature of the reaction was reduced. The unsaturated aldehyde, trans-2-decenal, stimulates BM3-F87G catalyzed oxidation of 4-fluorophenol through a cooperative active site binding mode that doesn't influence product distributions or coupling efficiencies, while 4-fluorophenol acts as a competitive inhibitor of aldehyde oxidation.

One-Pot Amide Bond Formation from Aldehydes and Amines via a Photoorganocatalytic Activation of Aldehydes.

PubMed

Papadopoulos, Giorgos N; Kokotos, Christoforos G

2016-08-19

A mild, one-pot, and environmentally friendly synthesis of amides from aldehydes and amines is described. Initially, a photoorganocatalytic reaction of aldehydes with di-isopropyl azodicarboxylate leads to an intermediate carbonyl imide, which can react with a variety of amines to afford the desired amides. The initial visible light-mediated activation of a variety of monosubstituted or disubstituted aldehydes is usually fast, occurring in a few hours. Following the photocatalytic reaction, addition of the primary amine at room temperature or the secondary amine at elevated temperatures leads to the corresponding amide from moderate to excellent yields without epimerization. This methodology was applied in the synthesis of Moclobemide, a drug against depression and social anxiety.

EMISSIONS OF ODOROUS ALDEHYDES FROM ALKYD PAINT

EPA Science Inventory

Aldehyde emissions are widely held responsible for the acrid after-odor of drying alkyd-based paint films. The aldehyde emissions from three different alkyd paints were measured in small environmental chambers. It was found that, for each alkyd paint applied, more than 2 mg of ...

Age-dependent neurodegeneration accompanying memory loss in transgenic mice defective in mitochondrial aldehyde dehydrogenase 2 activity.

PubMed

Ohsawa, Ikuroh; Nishimaki, Kiyomi; Murakami, Yayoi; Suzuki, Yuko; Ishikawa, Masahiro; Ohta, Shigeo

2008-06-11

Oxidative stress may underlie age-dependent memory loss and cognitive decline. Toxic aldehydes, including 4-hydroxy-2-nonenal (HNE), an end product of lipid peroxides, are known to accumulate in the brain in neurodegenerative disease. We have previously shown that mitochondrial aldehyde dehydrogenase 2 (ALDH2) detoxifies HNE by oxidizing its aldehyde group. To investigate the role of such toxic aldehydes, we produced transgenic mice, which expressed a dominant-negative form of ALDH2 in the brain. The mice had decreased ability to detoxify HNE in their cortical neurons and accelerated accumulation of HNE in the brain. Consequently, their lifespan was shortened and age-dependent neurodegeneration and hyperphosphorylation of tau were observed. Object recognition and Morris water maze tests revealed that the onset of cognitive impairment correlated with the degeneration, which was further accelerated by APOE (apolipoprotein E) knock-out; therefore, the accumulation of toxic aldehydes is by itself critical in the progression of neurodegenerative disease, which could be suppressed by ALDH2.

Amino Acid Degradations Produced by Lipid Oxidation Products.

PubMed

Hidalgo, Francisco J; Zamora, Rosario

2016-06-10

Differently to amino acid degradations produced by carbohydrate-derived reactive carbonyls, amino acid degradations produced by lipid oxidation products are lesser known in spite of being lipid oxidation a major source of reactive carbonyls in food. This article analyzes the conversion of amino acids into Strecker aldehydes, α-keto acids, and amines produced by lipid-derived free radicals and carbonyl compounds, as well as the role of lipid oxidation products on the reactions suffered by these compounds: the formation of Strecker aldehydes and other aldehydes from α-keto acids; the formation of Strecker aldehydes and olefins from amines; the formation of shorter aldehydes from Strecker aldehydes; and the addition reactions suffered by the olefins produced from the amines. The relationships among all these reactions and the effect of reaction conditions on them are discussed. This knowledge should contribute to better control food processing in order to favor the formation of desirable beneficial compounds and to inhibit the production of compounds with deleterious properties.

Fatty Aldehydes in Cyanobacteria Are a Metabolically Flexible Precursor for a Diversity of Biofuel Products

PubMed Central

Kaiser, Brett K.; Carleton, Michael; Hickman, Jason W.; Miller, Cameron; Lawson, David; Budde, Mark; Warrener, Paul; Paredes, Angel; Mullapudi, Srinivas; Navarro, Patricia; Cross, Fred; Roberts, James M.

2013-01-01

We describe how pathway engineering can be used to convert a single intermediate derived from lipid biosynthesis, fatty aldehydes, into a variety of biofuel precursors including alkanes, free fatty acids and wax esters. In cyanobacteria, long-chain acyl-ACPs can be reduced to fatty aldehydes, and then decarbonylated to alkanes. We discovered a cyanobacteria class-3 aldehyde-dehydrogenase, AldE, that was necessary and sufficient to instead oxidize fatty aldehyde precursors into fatty acids. Overexpression of enzymes in this pathway resulted in production of 50 to 100 fold more fatty acids than alkanes, and the fatty acids were secreted from the cell. Co-expression of acyl-ACP reductase, an alcohol-dehydrogenase and a wax-ester-synthase resulted in a third fate for fatty aldehydes: conversion to wax esters, which accumulated as intracellular lipid bodies. Conversion of acyl-ACP to fatty acids using endogenous cyanobacterial enzymes may allow biofuel production without transgenesis. PMID:23505484

Toxicity of polyunsaturated aldehydes of diatoms to Indo-Pacific bioindicator organism Echinometra mathaei.

PubMed

Sartori, Davide; Gaion, Andrea

2016-01-01

Although it is well known suitability of early developmental stages of sea urchin as recommended model for pollutant toxicity testing, little is known about the sensitivity of Indo-Pacific species Echinometra mathaei to polyunsaturated aldehydes. In this study, the effect of three short chain aldehydes, 2,4-decadienal (DD), 2,4-octadienal (OD) and 2,4-heptadienal (HD), normally found in many diatoms, such as Skeletonema costatum, Skeletonema marinoi and Thalassiosira rotula, was evaluated on larval development of E. mathaei embryos. Aldehydes affected larval development in a dose-dependent manner, in particular HD>OD>DD; the results of this study highlighted the higher sensitivity of this species toward aldehydes compared with data registered for other sea urchin species. In comparison with studies reported in the literature, contrasting results were observed during our tests; therefore, an increasing toxic effect was registered with decreasing the chain length of aldehydes. This work could provide new insights in the development of new toxicological assays toward most sensitive species.

Effect of selected aldehydes found in the corncob hemicellulose hydrolysate on the growth and xylitol fermentation of Candida tropicalis.

PubMed

Wang, Le; Tang, Pingwah; Fan, Xiaoguang; Yuan, Qipeng

2013-01-01

The effects of four aldehydes (furfural, 5-hydroxymethylfurfural, vanillin and syringaldehyde), which were found in the corncob hemicellulose hydrolysate, on the growth and xylitol fermentation of Candida tropicalis were investigated. The results showed that vanillin was the most toxic aldehyde for the xylitol fermentation, followed by syringaldehyde, furfural and 5-hydroxymethylfurfural. Moreover, the binary combination tests revealed that furfural amplified the toxicity of other aldehydes and the toxicities of other binary combinations without furfural were simply additive. Based on the fermentation experiments, it was demonstrated that the inhibition of aldehydes could be alleviated by prolonging the fermentation incubation, increasing the initial cell concentration, enhancing the initial pH value and minimizing the furfural levels in the hydrolysate evaporation process. The strategies that we proposed to suppress the inhibitory effects of the aldehydes successfully avoided the complicated and costly detoxifications. Our findings could be potentially adopted for the industrial xylitol fermentation from hydrolysates. © 2013 American Institute of Chemical Engineers.

Aldehyde dehydrogenase 7A1 (ALDH7A1) is a novel enzyme involved in cellular defense against hyperosmotic stress.

PubMed

Brocker, Chad; Lassen, Natalie; Estey, Tia; Pappa, Aglaia; Cantore, Miriam; Orlova, Valeria V; Chavakis, Triantafyllos; Kavanagh, Kathryn L; Oppermann, Udo; Vasiliou, Vasilis

2010-06-11

Mammalian ALDH7A1 is homologous to plant ALDH7B1, an enzyme that protects against various forms of stress, such as salinity, dehydration, and osmotic stress. It is known that mutations in the human ALDH7A1 gene cause pyridoxine-dependent and folic acid-responsive seizures. Herein, we show for the first time that human ALDH7A1 protects against hyperosmotic stress by generating osmolytes and metabolizing toxic aldehydes. Human ALDH7A1 expression in Chinese hamster ovary cells attenuated osmotic stress-induced apoptosis caused by increased extracellular concentrations of sucrose or sodium chloride. Purified recombinant ALDH7A1 efficiently metabolized a number of aldehyde substrates, including the osmolyte precursor, betaine aldehyde, lipid peroxidation-derived aldehydes, and the intermediate lysine degradation product, alpha-aminoadipic semialdehyde. The crystal structure for ALDH7A1 supports the enzyme's substrate specificities. Tissue distribution studies in mice showed the highest expression of ALDH7A1 protein in liver, kidney, and brain, followed by pancreas and testes. ALDH7A1 protein was found in the cytosol, nucleus, and mitochondria, making it unique among the aldehyde dehydrogenase enzymes. Analysis of human and mouse cDNA sequences revealed mitochondrial and cytosolic transcripts that are differentially expressed in a tissue-specific manner in mice. In conclusion, ALDH7A1 is a novel aldehyde dehydrogenase expressed in multiple subcellular compartments that protects against hyperosmotic stress by generating osmolytes and metabolizing toxic aldehydes.

Research on the Ordered Mesoporous Silica for Tobacco Harm Reduction

NASA Astrophysics Data System (ADS)

Wang, Y.; Y Li, Z.; Ding, J. X.; Hu, Z. J.; Liu, Z.; Zhou, G.; Huang, T. H.

2017-12-01

For reducting tobacco harm, this paper prepared an ordered mesoporous silica by using triblock copolymer Pluronic P123 as template. The property of this material was characterized by the X-ray scattering spectrum(XRD), Transmission electron microscopy(TEM), Scanning electron microscopy (SEM) and Nitrogen adsorption/desorption. Then this ordered mesoporous silica was added into the cigarette filter in order to researching its effect of cigarette harm index. The result shows that the feature of SBA-15 was grain morphology, ordered arrangement, tubular porous 2-D hexagonal structure. The application of SBA-15 in cigarette filter can selectively reduce harmful components in cigarette smoke such as crotonaldehyde, hydrogen cyanide, benzo pyrene and tar. The synthesized SBA-15 could properly reduce cigarette harm index.

Crude glycerol combustion: particulate, acrolein, and other volatile organic emissions

EPA Science Inventory

Crude glycerol is an abundant by-product of biodiesel production. As volumes of this potential waste grow, there is increasing interest in developing new value added uses. One possible use, as a boiler fuel for process heating, offers added advantages of energy integration and ...

Effects of Toluene, Acrolein and Vinyl Chloride on Motor Activity of Drosophila Melanogaster

EPA Science Inventory

The data generated by current high-throughput assays for chemical toxicity require information to link effects at molecular targets to adverse outcomes in whole animals. In addition, more efficient methods for testing volatile chemicals are needed. Here we begin to address these ...

A Novel Hypoxia Challenge Test Demonstrates Cardiovascular and Pulmonary Susceptibility to Acrolein Gas in Hypertensive Rats.

EPA Science Inventory

High levels of air pollution increase the risk of cardiovascular morbidity and mortality, especially in susceptible populations including those with hypertension. Stress tests are useful for manifesting latent effects of exposure, particularly at low concentrations, often when no...

Emissions from Electronic Cigarettes: Assessing Vapers' Intake of Toxic Compounds, Secondhand Exposures, and the Associated Health Impacts.

PubMed

Logue, Jennifer M; Sleiman, Mohamad; Montesinos, V Nahuel; Russell, Marion L; Litter, Marta I; Benowitz, Neal L; Gundel, Lara A; Destaillats, Hugo

2017-08-15

E-cigarettes likely represent a lower risk to health than traditional combustion cigarettes, but they are not innocuous. Recently reported emission rates of potentially harmful compounds were used to assess intake and predict health impacts for vapers and bystanders exposed passively. Vapers' toxicant intake was calculated for scenarios in which different e-liquids were used with various vaporizers, battery power settings and vaping regimes. For a high rate of 250 puff day -1 using a typical vaping regime and popular tank devices with battery voltages from 3.8 to 4.8 V, users were predicted to inhale formaldehyde (up to 49 mg day -1 ), acrolein (up to 10 mg day -1 ) and diacetyl (up to 0.5 mg day -1 ), at levels that exceeded U.S. occupational limits. Formaldehyde intake from 100 daily puffs was higher than the amount inhaled by a smoker consuming 10 conventional cigarettes per day. Secondhand exposures were predicted for two typical indoor scenarios: a home and a bar. Contributions from vaping to air pollutant concentrations in the home did not exceed the California OEHHA 8-h reference exposure levels (RELs), except when a high emitting device was used at 4.8 V. In that extreme scenario, the contributions from vaping amounted to as much as 12 μg m -3 formaldehyde and 2.6 μg m -3 acrolein. Pollutant concentrations in bars were modeled using indoor volumes, air exchange rates and the number of hourly users reported in the literature for U.S. bars in which smoking was allowed. Predicted contributions to indoor air levels were higher than those in the residential scenario. Formaldehyde (on average 135 μg m -3 ) and acrolein (28 μg m -3 ) exceeded the acute 1-h exposure REL for the highest emitting vaporizer/voltage combination. Predictions for these compounds also exceeded the 8-h REL in several bars when less intense vaping conditions were considered. Benzene concentrations in a few bars approached the 8-h REL, and diacetyl levels were close to the lower limit for occupational exposures. The integrated health damage from passive vaping was derived by computing disability-adjusted life years (DALYs) lost due to exposure to secondhand vapor. Acrolein was the dominant contributor to the aggregate harm. DALYs for the various device/voltage combinations were lower than-or comparable to-those estimated for exposures to secondhand and thirdhand tobacco smoke.

A Novel NADPH-Dependent Aldehyde Reductase Gene from Saccharomyces cerevisiae NRRL Y-12632 Involved in the Detoxification of Aldehyde Inhibitors Derived from Lignocellulosic Biomass Conversion

USDA-ARS?s Scientific Manuscript database

Aldehyde inhibitors such as furfural, 5-hydroxymethylfurfural (HMF), anisaldehyde, benzaldehyde, cinnamaldehyde, and phenylaldehyde are commonly generated during lignocellulosic biomass conversion process for low-cost cellulosic ethanol production that interferes with subsequent microbial growth and...

Draft Genome Sequence of Aldehyde-Degrading Strain Halomonas axialensis ACH-L-8

PubMed Central

Ye, Jun; Ren, Chong; Shan, Xiexie

2016-01-01

Halomonas axialensis ACH-L-8, a deep-sea strain isolated from the South China Sea, has the ability to degrade aldehydes. Here, we present an annotated draft genome sequence of this species, which could provide fundamental molecular information on the aldehydes-degrading mechanism. PMID:27081145

GRE2 from Scheffersomyces stipitis as an aldehyde reductase contributes tolerance to aldehyde inhibitors derived from lignocellulosic biomass

USDA-ARS?s Scientific Manuscript database

Scheffersomyces (Pichia) stipitis is one of the most promising yeasts for industrial bioethanol production from lignocellulosic biomass. S. stipitis is able to in situ detoxify aldehyde inhibitors [such as furfural and 5-hydroxymethylfurfural (HMF)] to less toxic corresponding alcohols. However, the...

Kinetic mechanism of an aldehyde reductase of Saccharomyces cerevisiae that relieves toxicity of furfural and 5-hydroxymethylfurfural

USDA-ARS?s Scientific Manuscript database

An effective means of relieving the toxicity of furan aldehydes, furfural (FFA) and 5-hydroxymethylfurfural (HMF), on fermenting organisms is essential for achieving efficient fermentation of lignocellulosic biomass to ethanol and other products. Ari1p, an aldehyde reductase from Saccharomyces cerev...

The carbonyl oxide-aldehyde complex: a new intermediate of the ozonolysis reaction

NASA Astrophysics Data System (ADS)

Cremer, Dieter; Kraka, Elfi; McKee, M. L.; Radharkrishnan, T. P.

1991-12-01

MP4(SDQ)/6-31G (d,p) calculations suggest that the ozonolysis of alkenes in solution phase does not proceed via carbonyl oxide, but via a dipole complex between aldehyde and carbonyl oxide, which is 9 kcal/mol more stable than the separated molecules. The dipole complex is probably formed in the solvent cage upon decomposition of primary ozonide to aldehyde and carbonyl oxide. Rotation of either aldehyde or carbonyl oxide in the solvent cage leads to an antiparallel alignment of molecular dipole moments and dipole-dipole attraction.

An Efficient Synthesis of 2-Substituted Benzimidazoles via Photocatalytic Condensation of o-Phenylenediamines and Aldehydes.

PubMed

Kovvuri, Jeshma; Nagaraju, Burri; Kamal, Ahmed; Srivastava, Ajay K

2016-10-10

A photocatalytic method has been developed for the efficient synthesis of functionalized benzimidazoles. This protocol involves photocatalytic condensation of o-phenylenediamines with various aldehydes using the Rose Bengal as photocatalyst. The method was found to be general and was successfully employed for accessing pharmaceutically important benzimidazoles by the condensation of aromatic, heteroaromatic and aliphatic aldehydes with o-phenylenediamines, in good-to-excellent yields. Notably, the method was found to be effective for the condensation of less reactive heterocyclic aldehydes with o-phenylenediamines.

Preparation of 3,5-disubstituted pyrazoles and isoxazoles from terminal alkynes, aldehydes, hydrazines, and hydroxylamine.

PubMed

Harigae, Ryo; Moriyama, Katsuhiko; Togo, Hideo

2014-03-07

The reaction of terminal alkynes with n-BuLi, and then with aldehydes, followed by the treatment with molecular iodine, and subsequently hydrazines or hydroxylamine provided the corresponding 3,5-disubstituted pyrazoles or isoxazoles in good yields with high regioselectivity, through the formations of propargyl secondary alkoxides and α-alkynyl ketones. The present reactions are one-pot preparation of 3,5-disubstituted pyrazoles from terminal alkynes, aldehydes, molecular iodine, and hydrazines, and 3,5-disubstituted isoxazoles from terminal alkynes, aldehydes, molecular iodine, and hydroxylamine.

Enantioselective direct α-amination of aldehydes via a photoredox mechanism: a strategy for asymmetric amine fragment coupling.

PubMed

Cecere, Giuseppe; König, Christian M; Alleva, Jennifer L; MacMillan, David W C

2013-08-07

The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated N-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine precursor obviates the need to employ a photoredox catalyst in this transformation. Importantly, this photoinduced transformation allows direct and enantioselective access to α-amino aldehyde products that do not require postreaction manipulation.

A Simple One-pot Conversion of Aldehydes and Ketones to Enals

PubMed Central

Valenta, Petr; Drucker, Natalie A.; Bode, Jeffrey W.; Walsh, Patrick J.

2009-01-01

A simple and efficient method to convert aldehydes into α,β-unsaturated aldehydes with a two-carbon homologation is presented. Hydroboration of ethoxy acetylene with BH3•SMe2 generates tris(ethoxyvinyl) borane. Transmetallation with diethylzinc, addition to aldehydes or ketones, and acidic workup affords enals. When the addition is quenched with anilinium hydrochloride, 1,2-dithioglycol, or acetic anhydride the unsaturated imine, dithiolane, or 1,1-diacetate is isolated in high yield. These transformations can be performed in a one-pot procedure. PMID:19419211

A modified Girard derivatizing reagent for universal profiling and trace analysis of aldehydes and ketones by electrospray ionization tandem mass spectrometry.

PubMed

Johnson, David W

2007-01-01

4-Hydrazino-N,N,N-trimethyl-4-oxobutanaminium iodide (HTMOB) is a modified Girard derivatizing reagent synthesized to improve the sensitivity of analysis of aldehydes and ketones with electrospray ionization tandem mass spectrometry. Compared with Girard T reagent the measured signal intensity increase is between 3.3 times (succinylacetone) and 7.0 times (17-hydroxyprogesterone). HTMOB is a universal profiling reagent for aldehydes and ketones. A neutral loss of 59 Da scan detects all aldehydes and ketones from acetone to corticosteroids. Applications described include the profiling of ketones, ketoacids and ketodiacids in the urine of children with ketosis and the profiling of long-chain aldehydes incorporated in plasma plasmalogens. Copyright (c) 2007 John Wiley & Sons, Ltd.

Myoglobin-Catalyzed Olefination of Aldehydes.

PubMed

Tyagi, Vikas; Fasan, Rudi

2016-02-12

The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon-carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α-diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E diastereoselectivity (92-99.9 % de). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl α-diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein-based catalysts. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A kinetic estimate of the free aldehyde content of aldoses

NASA Technical Reports Server (NTRS)

Dworkin, J. P.; Miller, S. L.; Bada, J. L. (Principal Investigator)

2000-01-01

The relative free aldehyde content of eight hexoses and four pentoses has been estimated within about 10% from the rate constants for their reaction with urazole (1,2,4-triazole-3,5-dione). These values of the percent free aldehyde are in agreement with those estimated from CD measurements, but are more accurate. The relative free aldehyde contents for the aldoses were then correlated to various literature NMR measurements to obtain the absolute values. This procedure was also done for three deoxyaldoses, which react much more rapidly than can be accounted for by the free aldehyde content. This difference in reactivity between aldoses and deoxyaldoses is due to the inductive effect of the H versus the OH on C-2'. This may help explain why deoxyribonucleosides hydrolyze much more rapidly than ribonucleosides.

Mechanistic Insights from Reaction of α-Oxiranyl-Aldehydes with Cyanobacterial Aldehyde Deformylating Oxygenase

PubMed Central

Das, Debasis; Ellington, Benjamin; Paul, Bishwajit; Marsh, E. Neil G.

2014-01-01

The biosynthesis of long-chain aliphatic hydrocarbons, which are derived from fatty acids, is widespread in Nature. The last step in this pathway involves the decarbonylation of fatty aldehydes to the corresponding alkanes or alkenes. In cyanobacteria this is catalyzed by an aldehyde deformylating oxygenase. We have investigated the mechanism of this enzyme using substrates bearing an oxirane ring adjacent to the aldehyde carbon. The enzyme catalyzed the deformylation of these substrates to produce the corresponding oxiranes. Performing the reaction in D2O allowed the facial selectivity of proton addition to be examined by 1H-NMR spectroscopy. The proton is delivered with equal probability to either face of the oxirane ring, indicating the formation of an oxiranyl radical intermediate that is free to rotate during the reaction. Unexpectedly, the enzyme also catalyzes a side reaction in which oxiranyl-aldehydes undergo tandem deformylation to furnish alkanes two carbons shorter. We present evidence that this involves the rearrangement of the intermediate oxiranyl radical formed in the first step, resulting an aldehyde that is further deformylated in a second step. These observations provide support for a radical mechanism for deformylation and, furthermore, allow the lifetime of the radical intermediate to be estimated based on prior measurements of rate constants for the rearrangement of oxiranyl radicals. PMID:24313866

Inhibition of human cytochrome P450 2E1 and 2A6 by aldehydes: structure and activity relationships.

PubMed

Kandagatla, Suneel K; Mack, Todd; Simpson, Sean; Sollenberger, Jill; Helton, Eric; Raner, Gregory M

2014-08-05

The purpose of this study was to probe active site structure and dynamics of human cytochrome P4502E1 and P4502A6 using a series of related short chain fatty aldehydes. Binding efficiency of the aldehydes was monitored via their ability to inhibit the binding and activation of the probe substrates p-nitrophenol (2E1) and coumarin (2A6). Oxidation of the aldehydes was observed in reactions with individually expressed 2E1, but not 2A6, suggesting alternate binding modes. For saturated aldehydes the optimum chain length for inhibition of 2E1 was 9 carbons (KI=7.8 ± 0.3 μM), whereas for 2A6 heptanal was most potent (KI=15.8 ± 1.1 μM). A double bond in the 2-position of the aldehyde significantly decreased the observed KI relative to the corresponding saturated compound in most cases. A clear difference in the effect of the double bond was observed between the two isoforms. With 2E1, the double bond appeared to remove steric constraints on aldehyde binding with KI values for the 5-12 carbon compounds ranging between 2.6 ± 0.1 μM and 12.8 ± 0.5 μM, whereas steric effects remained the dominant factor in the binding of the unsaturated aldehydes to 2A6 (observed KI values between 7.0 ± 0.5 μM and >1000 μM). The aldehyde function was essential for effective inhibition, as the corresponding carboxylic acids had very little effect on enzyme activity over the same range of concentrations, and branching at the 3-position of the aldehydes increased the corresponding KI value in all cases examined. The results suggest that a conjugated π-system may be a key structural determinant in the binding of these compounds to both enzymes, and may also be an important feature for the expansion of the active site volume in 2E1. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Inhibition of human Cytochrome P450 2E1 and 2A6 by aldehydes: Structure and activity relationships

PubMed Central

Kandagatla, Suneel K.; Mack, Todd; Simpson, Sean; Sollenberger, Jill; Helton, Eric; Raner, Gregory M.

2014-01-01

The purpose of this study was to probe active site structure and dynamics of human cytochrome P4502E1 and P4502A6 using a series of related short chain fatty aldehydes. Binding efficiency of the aldehydes was monitored via their ability to inhibit the binding and activation of the probe substrates p-nitrophenol (2E1) and coumarin (2A6). Oxidation of the aldehydes was observed in reactions with individually expressed 2E1, but not 2A6, suggesting alternate binding modes. For saturated aldehydes the optimum chain length for inhibition of 2E1 was 9 carbons (KI=7.8 ±0.3 μM), whereas for 2A6 heptanal was most potent (KI=15.8 ±1.1 μM). A double bond in the 2-position of the aldehyde significantly decreased the observed KI relative to the corresponding saturated compound in most cases. A clear difference in the effect of the double bond was observed between the two isoforms. With 2E1, the double bond appeared to remove steric constraints on aldehyde binding with KI values for the 5–12 carbon compounds ranging between 2.6 ± 0.1 μM and 12.8± 0.5 μM, whereas steric effects remained the dominant factor in the binding of the unsaturated aldehydes to 2A6 (observed KI values between 7.0± 0.5 μM and >1000 μM). The aldehyde function was essential for effective inhibition, as the corresponding carboxylic acids had very little effect on enzyme activity over the same range of concentrations, and branching at the 3-position of the aldehydes increased the corresponding KI value in all cases examined. The results suggest that a conjugated π-system may be a key structural determinant in the binding of these compounds to both enzymes, and may also be an important feature for the expansion of the active site volume in 2E1. PMID:24924949

A single exposure to acrolein desensitizes baroreflex responsiveness and increases cardiac arrhythmias in normotensive and hypertensive rats

EPA Science Inventory

Background – Short-term exposure to air pollutants has been linked to acute cardiovascular morbidity and mortality. Even in the absence of overt symptoms, pollutants can cause subtle disruptions of internal regulatory mechanisms, which maintain homeostatic balance, thereby reduci...

A FLUORESCENCE BASED ASSAY FOR DNA DAMAGE INDUCED BY TOXIC INDUSTRIAL CHEMICALS

EPA Science Inventory

One of the reported effects for exposure to many of the toxic industrial chemicals is DNA damage. The present study describes a simple, rapid and innovative assay to detect DNA damage resulting from exposure of surrogate DNA to toxic industrial chemicals (acrolein, allylamine, ch...

40 CFR Table 7 to Subpart Vvvvvv... - Partially Soluble HAP

Code of Federal Regulations, 2013 CFR

2013-07-01

.... Methylene chloride 75092 43. N-hexane 110543 44. N,N-dimethylaniline 121697 45. Naphthalene 91203 46...-Dichloroethylene (vinylidene chloride) 75354 5. 1,2-Dibromoethane 106934 6. 1,2-Dichloroethane (ethylene dichloride.... Acrolein 107028 15. Acrylonitrile 107131 16. Allyl chloride 107051 17. Benzene 71432 18. Benzyl chloride...

40 CFR Table 7 to Subpart Vvvvvv... - Partially Soluble HAP

Code of Federal Regulations, 2014 CFR

2014-07-01

.... Methylene chloride 75092 43. N-hexane 110543 44. N,N-dimethylaniline 121697 45. Naphthalene 91203 46...-Dichloroethylene (vinylidene chloride) 75354 5. 1,2-Dibromoethane 106934 6. 1,2-Dichloroethane (ethylene dichloride.... Acrolein 107028 15. Acrylonitrile 107131 16. Allyl chloride 107051 17. Benzene 71432 18. Benzyl chloride...

40 CFR Table 7 to Subpart Vvvvvv... - Partially Soluble HAP

Code of Federal Regulations, 2012 CFR

2012-07-01

.... Methylene chloride 75092 43. N-hexane 110543 44. N,N-dimethylaniline 121697 45. Naphthalene 91203 46...-Dichloroethylene (vinylidene chloride) 75354 5. 1,2-Dibromoethane 106934 6. 1,2-Dichloroethane (ethylene dichloride.... Acrolein 107028 15. Acrylonitrile 107131 16. Allyl chloride 107051 17. Benzene 71432 18. Benzyl chloride...

Hypoxia Stress Test Reveals Exaggerated Cardiovascular Effects in Hypertensive Rats after Exposure to the Air Pollutant Acrolein

EPA Science Inventory

Exposure to air pollution increases the risk of cardiovascular morbidity and mortality, especially in susceptible populations with cardiovascular disease. Stress tests are useful in assessing cardiovascular risk and manifesting latent effects of exposure. The goal of this study w...

Acrolein and other volatile organic emissions from the combustion of crude glycerol

EPA Science Inventory

Crude glycerol is an abundant by-product of biodiesel production. As volumes of this potential waste grow, there is increasing interest in developing new value added uses. One possible use, as a boiler fuel for process heating, offers added advantages of energy integration and f...

Selected constituents in the smoke of domestic low tar cigarettes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Griest, W. H.; Quincy, R. B.; Guerin, M. R.

Thirty-two brands of domestic commercial low tar and nicotine cigarettes were analyzed for their production of tar, nicotine, nitrogen oxides (as nitric oxide), hydrogen cyanide, acrolein, carbon monoxide and carbon dioxide under standard analytical smoking conditions. Results are compared with published data for certain brands.

Dobutamine cardiac "stress" test reveals increased arrhythmia risk in conscious rats after a single exposure to acrolein

EPA Science Inventory

Mild-to-moderate exercise is often used to stress the cardiovascular (CV) system of patients while monitoring them for electrocardiogram (ECG) abnormalities that may indicate underlying CV disease. We previously demonstrated that dobutamine, which increases heart rate (HR) and co...

Aldehyde Dehydrogenase 7A1 (ALDH7A1) Is a Novel Enzyme Involved in Cellular Defense against Hyperosmotic Stress*

PubMed Central

Brocker, Chad; Lassen, Natalie; Estey, Tia; Pappa, Aglaia; Cantore, Miriam; Orlova, Valeria V.; Chavakis, Triantafyllos; Kavanagh, Kathryn L.; Oppermann, Udo; Vasiliou, Vasilis

2010-01-01

Mammalian ALDH7A1 is homologous to plant ALDH7B1, an enzyme that protects against various forms of stress, such as salinity, dehydration, and osmotic stress. It is known that mutations in the human ALDH7A1 gene cause pyridoxine-dependent and folic acid-responsive seizures. Herein, we show for the first time that human ALDH7A1 protects against hyperosmotic stress by generating osmolytes and metabolizing toxic aldehydes. Human ALDH7A1 expression in Chinese hamster ovary cells attenuated osmotic stress-induced apoptosis caused by increased extracellular concentrations of sucrose or sodium chloride. Purified recombinant ALDH7A1 efficiently metabolized a number of aldehyde substrates, including the osmolyte precursor, betaine aldehyde, lipid peroxidation-derived aldehydes, and the intermediate lysine degradation product, α-aminoadipic semialdehyde. The crystal structure for ALDH7A1 supports the enzyme's substrate specificities. Tissue distribution studies in mice showed the highest expression of ALDH7A1 protein in liver, kidney, and brain, followed by pancreas and testes. ALDH7A1 protein was found in the cytosol, nucleus, and mitochondria, making it unique among the aldehyde dehydrogenase enzymes. Analysis of human and mouse cDNA sequences revealed mitochondrial and cytosolic transcripts that are differentially expressed in a tissue-specific manner in mice. In conclusion, ALDH7A1 is a novel aldehyde dehydrogenase expressed in multiple subcellular compartments that protects against hyperosmotic stress by generating osmolytes and metabolizing toxic aldehydes. PMID:20207735

Fluorescence lifetime analysis and effect of magnesium ions on binding of NADH to human aldehyde dehydrogenase 1

USDA-ARS?s Scientific Manuscript database

Aldehyde dehydrogenase 1 (ALDH1) catalyzes oxidation of toxic aldehydes to carboxylic acids. Physiologic levels of Mg2+ ions influence ALDH1 activity in part by increasing NADH binding affinity to the enzyme thus reducing activity. By using time-resolved fluorescence spectroscopy, we have resolved t...

Metabolism of 2-phenylethylamine to phenylacetic acid, via the intermediate phenylacetaldehyde, by freshly prepared and cryopreserved guinea pig liver slices.

PubMed

Panoutsopoulos, Georgios I

2004-01-01

2-Phenylethylamine is an endogenous amine, which acts as a neuromodulator of dopaminergic responses. Exogenous 2-phenylethylamine is found in certain foodstuffs and may cause toxic side-effects in susceptible individuals. The present investigation examined the metabolism of 2-phenylethylamine to phenylacetic acid, via phenylacetaldehyde, in freshly prepared and cryopreserved liver slices. Additionally, it compared the relative contribution of aldehyde oxidase, xanthine oxidase and aldehyde dehydrogenase by using specific inhibitors for each oxidizing enzyme. In freshly prepared and cryopreserved liver slices, phenylacetic acid was the main metabolite of 2-phenylethalamine. In freshly prepared liver slices, phenylacetic acid was completely inhibited by disulfiram (inhibitor of aldehyde dehydrogenase), whereas isovanillin (inhibitor of aldehyde oxidase) inhibited acid formation to a lesser extent and allopurinol (inhibitor of xanthine oxidase) had no effect. In cryopreserved liver slices, isovanillin inhibited phenylacetic acid by 85%, whereas disulfiram inhibited acid formation to a lesser extent and allopurinol had no effect. In liver slices, 2-phenylethylamine is rapidly oxidized to phenylacetic acid, via phenylacetaldehyde, by aldehyde dehydrogenase and aldehyde oxidase with no contribution from xanthine oxidase.

Nitrite promotes protein carbonylation and Strecker aldehyde formation in experimental fermented sausages: are both events connected?

PubMed

Villaverde, A; Ventanas, J; Estévez, M

2014-12-01

The role played by curing agents (nitrite, ascorbate) on protein oxidation and Strecker aldehyde formation is studied. To fulfill this objective, increasing concentrations of nitrite (0, 75 and 150ppm) and ascorbate (0, 250 and 500ppm) were added to sausages subjected to a 54day drying process. The concurrence of intense proteolysis, protein carbonylation and formation of Strecker aldehydes during processing of sausages suggests that α-aminoadipic semialdehyde (AAS) and γ-glutamic semialdehyde (GGS) may be implicated in the formation of Strecker aldehydes. The fact that nitrite (150ppm, ingoing amount) significantly promoted the formation of protein carbonyls at early stages of processing and the subsequent formation of Strecker aldehydes provides strength to this hypothesis. Ascorbate (125 and 250ppm) controlled the overall extent of protein carbonylation in sausages without declining the formation of Strecker aldehydes. These results may contribute to understanding the chemistry fundamentals of the positive influence of nitrite on the flavor and overall acceptability of cured muscle foods. Copyright © 2014 Elsevier Ltd. All rights reserved.

Aldehyde Dehydrogenases in Arabidopsis thaliana: Biochemical Requirements, Metabolic Pathways, and Functional Analysis.

PubMed

Stiti, Naim; Missihoun, Tagnon D; Kotchoni, Simeon O; Kirch, Hans-Hubert; Bartels, Dorothea

2011-01-01

Aldehyde dehydrogenases (ALDHs) are a family of enzymes which catalyze the oxidation of reactive aldehydes to their corresponding carboxylic acids. Here we summarize molecular genetic and biochemical analyses of selected ArabidopsisALDH genes. Aldehyde molecules are very reactive and are involved in many metabolic processes but when they accumulate in excess they become toxic. Thus activity of aldehyde dehydrogenases is important in regulating the homeostasis of aldehydes. Overexpression of some ALDH genes demonstrated an improved abiotic stress tolerance. Despite the fact that several reports are available describing a role for specific ALDHs, their precise physiological roles are often still unclear. Therefore a number of genetic and biochemical tools have been generated to address the function with an emphasis on stress-related ALDHs. ALDHs exert their functions in different cellular compartments and often in a developmental and tissue specific manner. To investigate substrate specificity, catalytic efficiencies have been determined using a range of substrates varying in carbon chain length and degree of carbon oxidation. Mutational approaches identified amino acid residues critical for coenzyme usage and enzyme activities.

Simultaneous derivatization/preconcentration of volatile aldehydes with a miniaturized fiber-packed sample preparation device designed for gas chromatographic analysis.

PubMed

Saito, Yoshihiro; Ueta, Ikuo; Ogawa, Mitsuhiro; Jinno, Kiyokatsu

2006-10-01

A novel in-needle sample preparation device has been developed for the determination of volatile aldehydes in gaseous samples. The needle device is designed for the gas chromatographic (GC) analysis of aldehydes and ketones commonly found in typical in-house environments. In order to prepare the extraction device, a bundle of polymer-coated filaments was longitudinally packed into a specially designed needle. Derivatization reactions were prompted by 2,4-dinitrophenylhydrazine (NDPH) included in the needle, and so the aldehydes and ketones were derivatized to the corresponding hydrazones and extracted with the extraction needle. A reproducible extraction needle preparation process was established, along with a repeatable derivatization/extraction process that ensures the successful determination of aldehydes. The storage performance of the extraction needle was also evaluated at room temperature for three days. The results demonstrate the successful application of the fiber-packed extraction device to the preparation of a gaseous sample of aldehydes, and the future possibility of applying the extraction device to the analysis of in-house environments.

Identification of predominant odorants in thai desserts flavored by smoking with "Tian Op", a traditional Thai scented candle.

PubMed

Watcharananun, Wanwarang; Cadwallader, Keith R; Huangrak, Kittiphong; Kim, Hun; Lorjaroenphon, Yaowapa

2009-02-11

"Tian Op", a traditional Thai scented candle, is used for the smoking and flavoring of sweets, cakes, and other desserts for the purpose of adding a unique aroma to the final product. Gas chromatography-olfactometry, aroma extract dilution analysis, and GC-MS were applied to identify the potent odorants in two types of traditional Thai desserts ("num dok mai" and "gleep lum duan") prepared using a Tian Op smoking process. On the basis of the results of AEDA and calculated odor-activity values, the predominant odorants in the Tian Op flavored desserts were vinyl ketones (C(5)-C(9)), n-aldehydes (C(5)-C(11)), (E)-2-unsaturated aldehydes (C(8)-C(11)), and omega-1-unsaturated aldehydes (C(8) and C(9)). Sensory studies of model mixtures confirmed the importance of n-aldehydes, omega-1-unsaturated aldehydes, and guaiacol as predominant odorants; however, the results showed that vinyl ketones and (E)-2-unsaturated aldehydes, despite having high odor-activity values, may be of only minor importance in the typical aroma profiles of traditional Tian Op smoked desserts.

Aldehyde Dehydrogenases in Arabidopsis thaliana: Biochemical Requirements, Metabolic Pathways, and Functional Analysis

PubMed Central

Stiti, Naim; Missihoun, Tagnon D.; Kotchoni, Simeon O.; Kirch, Hans-Hubert; Bartels, Dorothea

2011-01-01

Aldehyde dehydrogenases (ALDHs) are a family of enzymes which catalyze the oxidation of reactive aldehydes to their corresponding carboxylic acids. Here we summarize molecular genetic and biochemical analyses of selected Arabidopsis ALDH genes. Aldehyde molecules are very reactive and are involved in many metabolic processes but when they accumulate in excess they become toxic. Thus activity of aldehyde dehydrogenases is important in regulating the homeostasis of aldehydes. Overexpression of some ALDH genes demonstrated an improved abiotic stress tolerance. Despite the fact that several reports are available describing a role for specific ALDHs, their precise physiological roles are often still unclear. Therefore a number of genetic and biochemical tools have been generated to address the function with an emphasis on stress-related ALDHs. ALDHs exert their functions in different cellular compartments and often in a developmental and tissue specific manner. To investigate substrate specificity, catalytic efficiencies have been determined using a range of substrates varying in carbon chain length and degree of carbon oxidation. Mutational approaches identified amino acid residues critical for coenzyme usage and enzyme activities. PMID:22639603

Concentration of simple aldehydes by sulfite-containing double-layer hydroxide minerals: implications for biopoesis

NASA Technical Reports Server (NTRS)

Pitsch, S.; Krishnamurthy, R.; Arrhenius, G.; Bada, J. L. (Principal Investigator)

2000-01-01

Environmental conditions play an important role in conceptual studies of prebiotically relevant chemical reactions that could have led to functional biomolecules. The necessary source compounds are likely to have been present in dilute solution, raising the question of how to achieve selective concentration and to reach activation. With the assumption of an initial 'RNA World', the questions of production, concentration, and interaction of aldehydes and aldehyde phosphates, potential precursors of sugar phosphates, come into the foreground. As a possible concentration process for simple, uncharged aldehydes, we investigated their adduct formation with sulfite ion bound in the interlayer of positively charged expanding-sheet-structure double-layer hydroxide minerals. Minerals of this type, initially with chloride as interlayer counter anion, have previously been shown to induce concentration and subsequent aldolization of aldehyde phosphates to form tetrose, pentose, and hexose phosphates. The reversible uptake of the simple aldehydes formaldehyde, glycolaldehyde, and glyceraldehyde by adduct formation with the immobilized sulfite ions is characterized by equilibrium constants of K=1.5, 9, and 11, respectively. This translates into an observable uptake at concentrations exceeding 50 mM.

Effects of Schiff Base Formation and Aldol Condensation on the Determination of Aldehydes in Rice Wine Using GC-MS.

PubMed

Han, Ji Hye; Lee, Sang Mi; Kim, Young-Suk

2017-04-11

The Schiff base reaction and aldol condensation that occur during sample preparation can lead to the reduction of aldehyde content in the analysis of traditional Korean rice wine, makgeolli. The contents of aldehydes were decreased, whereas those of hydroxy carbonyl compounds were increased by increasing the pH. In the presence of added amino acids, the levels of aldehydes in makgeolli were reduced as the amount of the amino acid alanine increased. Also, the contents of hydroxyl carbonyl compounds were reduced by alanine addition as compared to the control. Therefore, the determination of aldehydes can be affected by pH and the amount of amino acids, which can vary during fermentation and storage of alcoholic beverages because pH and amino acids affect Schiff base formation and aldol condensation.

[Simultaneous analysis of aromatic aldehydes and coumarins with high pressure liquid chromatography. Application to wines and brandies stored in oak barrels].

PubMed

Salagoity-Auguste, M H; Tricard, C; Sudraud, P

1987-04-17

Aromatic aldehydes (vanillin, syringaldehyde, coniferaldehyde and sinapaldehyde) and coumarins (esculetin, umbelliferone, scopoletin and methylumbelliferone) are natural wood compounds. Storage of wines and brandies in oak barrels increases notably aldehydes and coumarins (particularly scopoletin) concentrations. These compounds were separated by high-performance liquid chromatography, on hydrocarbon bonded reversed-phase packings, with a water-acetonitrile elution gradient. They were first extracted from wines and brandies by diethyl ether and then injected on chromatographic column. A double detection was used to determine simultaneously aromatic aldehydes and coumarins by UV absorption and fluorescence respectively.

Manganese catalyzed reductive amination of aldehydes using hydrogen as a reductant.

PubMed

Wei, Duo; Bruneau-Voisine, Antoine; Valyaev, Dmitry A; Lugan, Noël; Sortais, Jean-Baptiste

2018-04-24

A one-pot two-step procedure was developed for the alkylation of amines via reductive amination of aldehydes using molecular dihydrogen as a reductant in the presence of a manganese pyridinyl-phosphine complex as a pre-catalyst. After the initial condensation step, the reduction of imines formed in situ is performed under mild conditions (50-100 °C) with 2 mol% of catalyst and 5 mol% of tBuOK under 50 bar of hydrogen. Excellent yields (>90%) were obtained for a large combination of aldehydes and amines (40 examples), including aliphatic aldehydes and amino-alcohols.

Enantioselective Direct α-Amination of Aldehydes via a Photoredox Mechanism: A Strategy for Asymmetric Amine Fragment Coupling

PubMed Central

Cecere, Giuseppe; Koenig, Christian M.; Alleva, Jennifer L.

2013-01-01

The direct, asymmetric α-amination of aldehydes has been accomplished via a combination of photoredox and organocatalysis. Photon-generated, nitrogen-centered radicals undergo enantioselective α-addition to catalytically formed chiral enamines to directly produce stable α-amino aldehyde adducts bearing synthetically useful amine substitution patterns. Incorporation of a photolabile group on the amine precursor obviates the need to employ a photoredox catalyst in this transformation. Importantly, this photoinduced transformation allows direct and enantioselective access to α-amino aldehyde products that do not require post-reaction manipulation. PMID:23869694

Protecting-group-free synthesis of amines: synthesis of primary amines from aldehydes via reductive amination.

PubMed

Dangerfield, Emma M; Plunkett, Catherine H; Win-Mason, Anna L; Stocker, Bridget L; Timmer, Mattie S M

2010-08-20

New methodology for the protecting-group-free synthesis of primary amines is presented. By optimizing the metal hydride/ammonia mediated reductive amination of aldehydes and hemiacetals, primary amines were selectively prepared with no or minimal formation of the usual secondary and tertiary amine byproduct. The methodology was performed on a range of functionalized aldehyde substrates, including in situ formed aldehydes from a Vasella reaction. These reductive amination conditions provide a valuable synthetic tool for the selective production of primary amines in fewer steps, in good yields, and without the use of protecting groups.

Enantioselective Organocatalytic Aminomethylation of Aldehydes: A Role for Ionic Interactions and Efficient Access to β2-Amino Acids

PubMed Central

Chi, Yonggui; Gellman, Samuel H.

2009-01-01

Organocatalytic Mannich addition of aldehydes to a formaldehyde-derived iminium species catalyzed by proline-derived chiral pyrrolidines provides β-amino aldehydes with ≥ 90% ee. Mechanistic analysis of the proline-catalyzed reactions suggests that non-hydrogen-bonded ionic interactions at the Mannich reaction transition state can influence stereochemical outcome. The β-amino aldehydes from our process bear a substituent adjacent to the carbonyl and can be efficiently converted to protected β2-amino acids, which are important building blocks for β-peptide foldamers that display useful biological activities. PMID:16719457

The first mammalian aldehyde oxidase crystal structure: insights into substrate specificity.

PubMed

Coelho, Catarina; Mahro, Martin; Trincão, José; Carvalho, Alexandra T P; Ramos, Maria João; Terao, Mineko; Garattini, Enrico; Leimkühler, Silke; Romão, Maria João

2012-11-23

Aldehyde oxidases have pharmacological relevance, and AOX3 is the major drug-metabolizing enzyme in rodents. The crystal structure of mouse AOX3 with kinetics and molecular docking studies provides insights into its enzymatic characteristics. Differences in substrate and inhibitor specificities can be rationalized by comparing the AOX3 and xanthine oxidase structures. The first aldehyde oxidase structure represents a major advance for drug design and mechanistic studies. Aldehyde oxidases (AOXs) are homodimeric proteins belonging to the xanthine oxidase family of molybdenum-containing enzymes. Each 150-kDa monomer contains a FAD redox cofactor, two spectroscopically distinct [2Fe-2S] clusters, and a molybdenum cofactor located within the protein active site. AOXs are characterized by broad range substrate specificity, oxidizing different aldehydes and aromatic N-heterocycles. Despite increasing recognition of its role in the metabolism of drugs and xenobiotics, the physiological function of the protein is still largely unknown. We have crystallized and solved the crystal structure of mouse liver aldehyde oxidase 3 to 2.9 Å. This is the first mammalian AOX whose structure has been solved. The structure provides important insights into the protein active center and further evidence on the catalytic differences characterizing AOX and xanthine oxidoreductase. The mouse liver aldehyde oxidase 3 three-dimensional structure combined with kinetic, mutagenesis data, molecular docking, and molecular dynamics studies make a decisive contribution to understand the molecular basis of its rather broad substrate specificity.

Initial steps of the peroxidase-catalyzed polymerization of coniferyl alcohol and/or sinapyl aldehyde: capillary zone electrophoresis study of pH effect.

PubMed

Fournand, David; Cathala, Bernard; Lapierre, Catherine

2003-01-01

Capillary zone electrophoresis has been used to monitor the first steps of the dehydrogenative polymerization of coniferyl alcohol, sinapyl aldehyde, or a mixture of both, catalyzed by the horseradish peroxidase (HRP)-H(2)O(2) system. When coniferyl alcohol was the unique HRP substrate, three major dimers were observed (beta-5, beta-beta, and beta-O-4 interunit linkages) and their initial formation velocity as well as their relative abundance varied with pH. The beta-O-4 interunit linkage was thus slightly favored at lower pH values. In contrast, sinapyl aldehyde turned out to be a very poor substrate for HRP except in basic conditions (pH 8). The major dimer observed was the beta,beta'-di-sinapyl aldehyde, a red-brown exhibiting compound which might partly participate in the red coloration usually observed in cinnamyl alcohol dehydrogenase-deficient angiosperms. Finally, when a mixture of coniferyl alcohol and sinapyl aldehyde was used, it looked as if sinapyl aldehyde became a very good substrate for HRP. Indeed, coniferyl alcohol turned out to serve as a redox mediator (i.e. "shuttle oxidant") for the sinapyl aldehyde incorporation in the lignin-like polymer. This means that in particular conditions the specificity of oxidative enzymes might not hinder the incorporation of poor substrates into the growing lignin polymer.

RP-HPLC-fluorescence analysis of aliphatic aldehydes: application to aldehyde-generating enzymes HACL1 and SGPL1

PubMed Central

Mezzar, Serena; de Schryver, Evelyn; Van Veldhoven, Paul P.

2014-01-01

Long-chain aldehydes are commonly produced in various processes, such as peroxisomal α-oxidation of long-chain 3-methyl-branched and 2-hydroxy fatty acids and microsomal breakdown of phosphorylated sphingoid bases. The enzymes involved in the aldehyde-generating steps of these processes are 2-hydroxyacyl-CoA lyase (HACL1) and sphingosine-1-phosphate lyase (SGPL1), respectively. In the present work, nonradioactive assays for these enzymes were developed employing the Hantzsch reaction. Tridecanal (C13-al) and heptadecanal (C17-al) were selected as model compounds and cyclohexane-1,3-dione as 1,3-diketone, and the fluorescent derivatives were analyzed by reversed phase (RP)-HPLC. Assay mixture composition, as well as pH and heating, were optimized for C13-al and C17-al. Under optimized conditions, these aldehydes could be quantified in picomolar range and different long-chain aldehyde derivatives were well resolved with a linear gradient elution by RP-HPLC. Aldehydes generated by recombinant enzymes could easily be detected via this method. Moreover, the assay allowed to document activity or deficiency in tissue homogenates and fibroblast lysates without an extraction step. In conclusion, a simple, quick, and cheap assay for the study of HACL1 and SGPL1 activities was developed, without relying on expensive mass spectrometric detectors or radioactive substrates. PMID:24323699

9,10-Phenanthrenequinone as a mass-tagging reagent for ultra-sensitive liquid chromatography-tandem mass spectrometry assay of aliphatic aldehydes in human serum.

PubMed

El-Maghrabey, Mahmoud; Kishikawa, Naoya; Kuroda, Naotaka

2016-09-02

9,10-Phenanthrenequinone (PQ) was successfully used as a new mass-tagging reagent for sensitive labeling of aliphatic aldehydes (C3-C10) prior liquid chromatography-electrospray ionization-tandem mass spectrometry (LC/ESI-MS/MS). This reagent could overcome the drawbacks of previous amine or hydrazine-based reagents, such as lower sensitivity, formation of two stereoisomeric reaction products for each single analyte, need for longer derivatization time, and poor reactivity with aliphatic aldehydes. The PQ-aldehyde derivatives exhibited intense [M+H](+) and a common product ion with ESI in the positive-ion mode. The derivatives were monitored at the transition of [M+H](+)→m/z 231.9 with detection limits from 4.0 to 100 pM (signal to noise ratio=3). 3-Phenylpropanal was used as an internal standard (IS) and the separation of the eight aldehydes and IS was achieved in less than 10min employing gradient elution with methanol and ammonium formate buffer (20mM, pH 4.0). The method employed salting out liquid-liquid extraction for aliphatic aldehydes form serum for the first time with excellent recoveries (92.6-110.8%). The developed method was validated and applied for quantification of the target aldehydes in serum of healthy volunteers (n=14). Copyright © 2016 Elsevier B.V. All rights reserved.

Aldehyde-containing urea-absorbing polysaccharides

NASA Technical Reports Server (NTRS)

Mueller, W. A.; Hsu, G. C.; Marsh, H. E., Jr. (Inventor)

1977-01-01

A novel aldehyde containing polymer (ACP) is prepared by reaction of a polysaccharide with periodate to introduce aldehyde groups onto the C2 - C3 carbon atoms. By introduction of ether and ester groups onto the pendant primary hydroxyl solubility characteristics are modified. The ACP is utilized to absorb nitrogen bases such as urea in vitro or in vivo.

The rhodium catalyzed three-component reaction of diazoacetates, titanium(IV) alkoxides and aldehydes.

PubMed

Lu, Chong-Dao; Liu, Hui; Chen, Zhi-Yong; Hu, Wen-Hao; Mi, Ai-Qiao

2005-05-28

The rhodium(II)-catalyzed three-component reaction of diazoacetates, titanium alkoxides and aldehydes is shown to give alpha-alkoxyl-beta-hydroxyl acid derivatives; the novel C-C bond formation reaction is proposed to occur through oxonium ylides derived from diazo compounds and titanium alkoxides, and followed by intermolecular trapping by aldehydes.

OZONE REACTION WITH N-ALDEHYDES (N=4-10), BENZALDEHYDE, ETHANOL, ISOPROPANOL, AND N-PROPANOL ADSORBED ON A DUAL-BED GRAPHITIZED CARBON/CARBON MOLECULAR SIEVE ADSORBENT CARTRIDGE

EPA Science Inventory

Ozone reacts with n-aldehydes (n = 4 - 10), benzaldehyde, ethanol, isopropanol, and n-propanol adsorbed on a dual-bed graphitized carbon/carbon molecular sieve adsorbent cartridge. Destruction of n-aldehydes increases with n number and with ozone concentration. In some samp...

Palladium-catalyzed, pyrrolidine-mediated arylmethylation of ketones and aldehydes with coumarinyl(methyl) acetates.

PubMed

Cattopadhyay, Kalicharan; Recio, Antonio; Tunge, Jon A

2012-09-14

We report the palladium-catalyzed, pyrrolidine-mediated α-benzylation of enamines generated from aldehydes and ketones. The method allows for direct coupling of medicinally relevant coumarin moieties with aldehydes and ketones in good yield under mild conditions. The reaction is believed to proceed via a Pd-π-benzyl complex generated from (coumarinyl)methyl acetates.

Kinetics of forming aldehydes in frying oils and their distribution in French fries revealed by LC-MS-based chemometrics

USDA-ARS?s Scientific Manuscript database

Aldehydes are major secondary lipid oxidation products (LOPs) from heating vegetable oils and deep frying. The routes and reactions that generate aldehydes have been extensively investigated, but the sequences and kinetics of their formation in oils are poorly defined. In this study, a platform comb...

Aldehydic load and aldehyde dehydrogenase 2 profile during the progression of post-myocardial infarction cardiomyopathy: benefits of Alda-1

PubMed Central

Gomes, Katia M.S.; Bechara, Luiz R.G.; Lima, Vanessa M.; Ribeiro, Márcio A.C.; Campos, Juliane C.; Dourado, Paulo M.; Kowaltowski, Alicia J.; Mochly-Rosen, Daria; Ferreira, Julio C.B.

2015-01-01

Background/Objectives We previously demonstrated that reducing cardiac aldehydic load by aldehyde dehydrogenase 2 (ALDH2), a mitochondrial enzyme responsible for metabolizing the major lipid peroxidation product, protects against acute ischemia/reperfusion injury and chronic heart failure. However, time-dependent changes in ALDH2 profile, aldehydic load and mitochondrial bioenergetics during progression of post-myocardial infarction (post-MI) cardiomyopathy is unknown and should be established to determine the optimal time window for drug treatment. Methods Here we characterized cardiac ALDH2 activity and expression, lipid peroxidation, 4-hydroxy-2-nonenal (4-HNE) adduct formation, glutathione pool and mitochondrial energy metabolism and H2O2 release during the 4 weeks after permanent left anterior descending (LAD) coronary artery occlusion in rats. Results We observed a sustained disruption of cardiac mitochondrial function during the progression of post-MI cardiomyopathy, characterized by >50% reduced mitochondrial respiratory control ratios and up to 2 fold increase in H2O2 release. Mitochondrial dysfunction was accompanied by accumulation of cardiac and circulating lipid peroxides and 4-HNE protein adducts and down-regulation of electron transport chain complexes I and V. Moreover, increased aldehydic load was associated with a 90% reduction in cardiac ALDH2 activity and increased glutathione pool. Further supporting an ALDH2 mechanism, sustained Alda-1 treatment (starting 24hrs after permanent LAD occlusion surgery) prevented aldehydic overload, mitochondrial dysfunction and improved ventricular function in post-MI cardiomyopathy rats. Conclusion Taken together, our findings demonstrate a disrupted mitochondrial metabolism along with an insufficient cardiac ALDH2-mediated aldehyde clearance during the progression of ventricular dysfunction, suggesting a potential therapeutic value of ALDH2 activators during the progression of post-myocardial infarction cardiomyopathy. PMID:25464432

The activity of the artemisinic aldehyde Δ11(13) reductase promoter is important for artemisinin yield in different chemotypes of Artemisia annua L.

PubMed

Yang, Ke; Monfared, Sajad Rashidi; Monafared, Rashidi Sajad; Wang, Hongzhen; Lundgren, Anneli; Brodelius, Peter E

2015-07-01

The artemisinic aldehyde double bond reductase (DBR2) plays an important role in the biosynthesis of the antimalarial artemisinin in Artemisia annua. Artemisinic aldehyde is reduced into dihydroartemisinic aldehyde by DBR2. Artemisinic aldehyde can also be oxidized by amorpha-4,11-diene 12-hydroxylase and/or aldehyde dehydrogenase 1 to artemisinic acid, a precursor of arteannuin B. In order to better understand the effects of DBR2 expression on the flow of artemisinic aldehyde into either artemisinin or arteannuin B, we determined the content of dihydroartemisinic aldehyde, artemisinin, artemisinic acid and arteannuin B content of A. annua varieties sorted into two chemotypes. The high artemisinin producers (HAPs), which includes the '2/39', 'Chongqing' and 'Anamed' varieties, produce more artemisinin than arteannuin B; the low artemisinin producers (LAPs), which include the 'Meise', 'Iran#8', 'Iran#14', 'Iran#24' and 'Iran#47' varieties, produce more arteannuin B than artemisinin. Quantitative PCR showed that the relative expression of DBR2 was significantly higher in the HAP varieties. We cloned and sequenced the promoter of the DBR2 gene from varieties of both the LAP and the HAP groups. There were deletions/insertions in the region just upstream of the ATG start codon in the LAP varities, which might be the reason for the different promoter activities of the HAP and LAP varieties. The relevance of promoter variation, DBR2 expression levels and artemisinin biosynthesis capabilities are discussed and a selection method for HAP varieties with a DNA marker is suggested. Furthermore, putative cis-acting regulatory elements differ between the HAP and LAP varieties.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rock, C.D.; Zeevaart, J.A.D.

Previous {sup 18}O labeling studies of abscisic acid (ABA) have shown that apple (Malus domestica Borkh. cv Granny Smith) fruits synthesize a majority of ({sup 18}O)ABA with the label incorporated in the 1{prime}-hydroxyl position and unlabeled in the carboxyl group (JAD Zeevaart, TG Heath, DA Gage (1989) Plant Physiol 91: 1594-1601). It was proposed that exchange of {sup 18}O in the side chain with the medium occurred at an aldehyde intermediate stage of ABA biosynthesis. We have isolated ABA-aldehyde and 1{prime}-4{prime}-trans-ABA-diol (ABA-trans-diol) from {sup 18}O-labeled apple fruit tissue and measured the extent and position of {sup 18}O incorporation by tandemmore » mass spectrometry. {sup 18}O-Labeling patterns of ABA-aldehyde, ABA-trans-diol, and ABA indicate that ABA-aldehyde is a precursor to, and ABA-trans-diol a catabolite of, ABA. Exchange of {sup 18}O in the carbonyl of ABA-aldehyde can be the cause of loss of {sup 18}O from the side chain of ({sup 18}O)ABA. Results of feeding experiments with deuterated substrates provide further support for the precursor-product relationship of ABA-aldehyde {yields} ABA {yields} ABA-trans-diol. The ABA-aldehyde and ABA-trans-diol contents of fruits and leaves were low, approximately 1 and 0.02 nanograms per gram fresh weight for ABA-aldehyde and ABA-trans-diol, respectively, while ABA levels in fruits ranged from 10 to 200 nanograms per gram fresh weight. ABA biosynthesis was about 10-fold lower in fruits than in leaves. In fruits, the majority of ABA was conjugated to {beta}-D-glucopyranosyl abscisate, whereas in leaves ABA was mainly hydroxylated to phaseic acid. Parallel pathways for ABA and trans-ABA biosynthesis and conjugation in fruits and leaves are proposed.« less

Effect of peptide aldehydes with IL-1 beta converting enzyme inhibitory properties on IL-1 alpha and IL-1 beta production in vitro.

PubMed

Németh, K; Patthy, M; Fauszt, I; Széll, E; Székely, J I; Bajusz, S

1995-12-01

Tripeptide and pentapeptide aldehydes as substrate-base inhibitors of cysteine proteases were designed in our laboratory for the inhibition of interleukin-1 beta converting enzyme (ICE), a recently described cysteine protease responsible for the processing of IL-1 beta. The biological effectivity of the peptide aldehydes was studied in THP-1 cells and human whole blood. The released and cell-associated IL-1 alpha and IL-1 beta levels were determined by ELISA from the supernatants and cell lysates, respectively. The total IL-1 like bioactivity was assayed by the D10 G4.1 cell proliferation method. The tripeptide aldehyde (Z-Val-His-Asp-H) and pentapeptide aldehyde (Eoc-Ala-Tyr-Val-Ala-Asp-H) significantly reduced IL-1 beta levels in the supernatants in relatively high concentrations (10-100 microM), but the IL-1 alpha release was unaffected by these peptides. However, a considerable decrease in the cell-associated IL-1 beta and IL-1 alpha levels was observed. N-terminal extension of the tripeptide aldehyde yielded even more potent inhibitors. Amino acid substitution at the P2 position did not cause considerable changes in the inhibitory activity. The peptide aldehydes suppressed the IL-1 beta production in a reversible manner, whereas dexamethasone, a glucocorticoid, had a prolonged inhibitory effect. The inhibitory effect of these peptides and that of dexamethasone appeared to be additive. These findings indicate that these peptide aldehydes might be used as IL-beta inhibitory agents in experimental models in which IL-1 beta is a key mediator or ICE is implicated.

Direct enzyme assay evidence confirms aldehyde reductase function of Ydr541cp and Ygl039wp from Saccharomyces cerevisiae.

PubMed

Moon, Jaewoong; Liu, Z Lewis

2015-04-01

The aldehyde reductase gene ARI1 is a recently characterized member of an intermediate subfamily within the short-chain dehydrogenase/reductase (SDR) superfamily that clarified mechanisms of in situ detoxification of 2-furaldehyde and 5-hydroxymethyl-2-furaldehyde by Saccharomyces cerevisiae. Uncharacterized open reading frames (ORFs) are common among tolerant candidate genes identified for lignocellulose-to-advanced biofuels conversion. This study presents partially purified proteins of two ORFs, YDR541C and YGL039W, and direct enzyme assay evidence against aldehyde-inhibitory compounds commonly encountered during lignocellulosic biomass fermentation processes. Each of the partially purified proteins encoded by these ORFs showed a molecular mass of approximately 38 kDa, similar to Ari1p, a protein encoded by aldehyde reductase gene. Both proteins demonstrated strong aldehyde reduction activities toward 14 aldehyde substrates, with high levels of reduction activity for Ydr541cp toward both aromatic and aliphatic aldehydes. While Ydr541cp was observed to have a significantly higher specific enzyme activity at 20 U/mg using co-factor NADPH, Ygl039wp displayed a NADH preference at 25 U/mg in reduction of butylaldehyde. Amino acid sequence analysis identified a characteristic catalytic triad, Ser, Tyr and Lys; a conserved catalytic motif of Tyr-X-X-X-Lys; and a cofactor-binding sequence motif, Gly-X-X-Gly-X-X-Ala, near the N-terminus that are shared by Ydr541cp, Ygl039wp, Yol151wp/GRE2 and Ari1p. Findings of aldehyde reductase genes contribute to the yeast gene annotation and aids development of the next-generation biocatalyst for advanced biofuels production. Copyright © 2015 John Wiley & Sons, Ltd.

The Pivotal Role of Aldehyde Toxicity in Autism Spectrum Disorder: The Therapeutic Potential of Micronutrient Supplementation

PubMed Central

Jurnak, Frances

2015-01-01

Autism spectrum disorder (ASD) is characterized by social and communication impairments as well as by restricted, repetitive patterns of behavior and interests. Genomic studies have not revealed dominant genetic errors common to all forms of ASD. So ASD is assumed to be a complex disorder due to mutations in hundreds of common variants. Other theories argue that spontaneous DNA mutations and/or environmental factors contribute to as much as 50% of ASD. In reviewing potential genetic linkages between autism and alcoholism, it became apparent that all theories of ASD are consistent with aldehyde toxicity, in which endogenous and exogenous aldehydes accumulate as a consequence of mutations in key enzymes. Aldehyde toxicity is characterized by cell-localized, micronutrient deficiencies in sulfur-containing antioxidants, thiamine (B1), pyridoxine (B6), folate, Zn2+, possibly Mg2+, and retinoic acid, causing oxidative stress and a cascade of metabolic disturbances. Aldehydes also react with selective cytosolic and membrane proteins in the cell of origin; then some types migrate to damage neighboring cells. Reactive aldehydes also form adducts with DNA, selectively mutating bases and inducing strand breakage. This article reviews the relevant genomic, biochemical, and nutritional literature, which supports the central hypothesis that most ASD symptoms are consistent with symptoms of aldehyde toxicity. The hypothesis represents a paradigm shift in thinking and has profound implications for clinical detection, treatment, and even prevention of ASD. Insight is offered as to which neurologically afflicted children might successfully be treated with micronutrients and which children are unlikely to be helped. The aldehyde toxicity hypothesis likely applies to other neurological disorders. PMID:27330305

Synthesis and accumulation of aromatic aldehydes in an engineered strain of Escherichia coli.

PubMed

Kunjapur, Aditya M; Tarasova, Yekaterina; Prather, Kristala L J

2014-08-20

Aromatic aldehydes are useful in numerous applications, especially as flavors, fragrances, and pharmaceutical precursors. However, microbial synthesis of aldehydes is hindered by rapid, endogenous, and redundant conversion of aldehydes to their corresponding alcohols. We report the construction of an Escherichia coli K-12 MG1655 strain with reduced aromatic aldehyde reduction (RARE) that serves as a platform for aromatic aldehyde biosynthesis. Six genes with reported activity on the model substrate benzaldehyde were rationally targeted for deletion: three genes that encode aldo-keto reductases and three genes that encode alcohol dehydrogenases. Upon expression of a recombinant carboxylic acid reductase in the RARE strain and addition of benzoate during growth, benzaldehyde remained in the culture after 24 h, with less than 12% conversion of benzaldehyde to benzyl alcohol. Although individual overexpression results demonstrated that all six genes could contribute to benzaldehyde reduction in vivo, additional experiments featuring subset deletion strains revealed that two of the gene deletions were dispensable under the conditions tested. The engineered strain was next investigated for the production of vanillin from vanillate and succeeded in preventing formation of the byproduct vanillyl alcohol. A pathway for the biosynthesis of vanillin directly from glucose was introduced and resulted in a 55-fold improvement in vanillin titer when using the RARE strain versus the wild-type strain. Finally, synthesis of the chiral pharmaceutical intermediate L-phenylacetylcarbinol (L-PAC) was demonstrated from benzaldehyde and glucose upon expression of a recombinant mutant pyruvate decarboxylase in the RARE strain. Beyond allowing accumulation of aromatic aldehydes as end products in E. coli, the RARE strain expands the classes of chemicals that can be produced microbially via aldehyde intermediates.

Quantitative analysis of aldehydes in canned vegetables using static headspace-gas chromatography-mass spectrometry.

PubMed

Serrano, María; Gallego, Mercedes; Silva, Manuel

2017-11-17

Volatile aldehydes appear in canned vegetables as constituents and some of them can also be present as disinfection by-products (DBPs) because of the contact between vegetables and treated water. This paper describes two static headspace-gas chromatography-mass spectrometry (SHS-GC-MS) methods to determine 15 aldehydes in both the solid and the liquid phases of canned vegetables. The treatment for both phases of samples was carried out simultaneously into an SHS unit, including the leaching of the aldehydes (from the vegetable), their derivatization and volatilization of the oximes formed. Detection limits were obtained within the range of 15-400μg/kg and 3-40μg/L for aldehydes in the solid and the liquid phases of the food, respectively. The relative standard deviation was lower than 7% -for the whole array of the target analytes-, the trueness evaluated by recovery experiments provided %recoveries between 89 and 99% and short- and long-term stability studies indicated there was no significant variation in relative peak areas of all aldehydes in both phases of canned vegetables after their storing at 4°C for two weeks. The study of the origin of the 15 aldehydes detected between both phases of canned vegetables showed that: i) the presence of 13 aldehydes -at average concentrations of 2.2-39μg/kg and 0.25-71μg/L for the solid and the liquid phases, respectively- is because they are natural constituents of vegetables; and ii) the presence of glyoxal and methylglyoxal -which are mainly found in the liquid phase (average values, 1.4-4.1μg/L)- is ascribed to the use of treated water, thereby being DBPs. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of a pair of differential H/D isotope-coded derivatization reagents d(0)/d(3)-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine and its application for determination of aldehydes in selected aquatic products by liquid chromatography-tandem mass spectrometry.

PubMed

Sun, Zhiwei; Wang, Xiaoxiang; Cai, Yiping; Fu, Junqing; You, Jinmao

2014-03-01

A new pair of derivatization reagents, d0-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine (d0-MPIA) and d3-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine (d3-MPIA) have been designed and synthesized. It was successfully used to label aliphatic aldehydes and the aldehyde derivatives were analyzed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The new isotope-coded reagents could easily label aldehydes under acidic conditions in the presence of NaCNBH3. The target derivatives exhibited intense [M+H](+) and regular product ions with electrospray ionization source in positive mode. The d0/d3-MPIA-aldehydes were monitored by the transitions of [M+H](+)→m/z 322 and [M+H](+)→m/z 165, and the obtained detection limits were in the range of 0.18-15.9 pg/mL at signal to noise ratio of 3. The global isotope internal standard technology was employed for quantification analysis with d3-MPIA-aldehyde as internal standard for corresponding d0-MPIA-aldehyde. Excellent linear responses for relative quantification were observed in the range of 1/10-10/1 with coefficients >0.998. The developed method has been applied to the quantification of aliphatic aldehydes in selected aquatic products with RSD<3.6% and recoveries >85.2%. © 2013 Elsevier B.V. All rights reserved.

Enantioselective construction of quaternary stereogenic carbon atoms by the Lewis base catalyzed additions of silyl ketene imines to aldehydes.

PubMed

Denmark, Scott E; Wilson, Tyler W; Burk, Matthew T

2014-07-21

Silyl ketene imines derived from a variety of α-branched nitriles have been developed as highly useful reagents for the construction of quaternary stereogenic centers via the aldol addition reaction. In the presence of SiCl4 and the catalytic action of a chiral phosphoramide, silyl ketene imines undergo extremely rapid and high yielding addition to a wide variety of aromatic aldehydes with excellent diastereo- and enantioselectivity. Of particular note are the high yields and selectivities obtained from electron-rich, electron-poor, and hindered aldehydes. Linear aliphatic aldehydes did react with good diastereo- and enantioselectivity in the presence of nBu4N(+)I(-), but branched aldehydes were much less reactive. Semiempirical calculations provided a rationalization of the observed diastereo- and enantioselectivity via open transitions states. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silk fiber for in-tube solid-phase microextraction to detect aldehydes by chemical derivatization.

PubMed

Wang, Xiuqin; Pan, Lei; Feng, Juanjuan; Tian, Yu; Luo, Chuannan; Sun, Min

2017-11-03

Aldehydes are the potentially damaging pollutants in the environment, but it is difficult to be determined due to the low concentration level. Therefore, to accurate analysis of aldehydes, it is important for efficient sample preparation with selective enrichment and rapid separation. Environmentally friendly silk fiber as adsorbent material was directly applied to develop in-tube solid-phase microextraction for analyzing aqueous samples combined with high performance liquid chromatography. 2,4-Dinitrophenylhydrazine as a derivative reagent was used for chemical derivatization of aldehydes before extraction. Under optimum conditions, an online analysis method was built with the limits of detection in the range of 0.005-0.01μgL -1 and the linearity in the range of 0.03-10μgL -1 . Three aldehydes were determined in two real samples, and the relative recoveries were in the range of 95-102%. Copyright © 2017 Elsevier B.V. All rights reserved.

Sinterable Ceramic Powders from Laser-Heated Gases.

DTIC Science & Technology

1988-02-01

ether . carboxylic acid. and aldehyde clases: water is also included.Acrigto William and Goodman.’ a single crystalline sili- The single-crstalline...represent commonly available organic families, Including aliphatic and aromatic hydrocarbons, chlorides, ethers , ketones , esters, alcohols, aldehydes...Hydrocarbons Ketone Amine Chlorides Low-alcohols 8f . Ether Ester - _Aldehyde Ether Ketones High-alcohols 04 Carboxylic Ester I acid Ether o . Nitrile

Regioselectivity switch in chiral amine-catalysed asymmetric addition of aldehydes to reactive enals.

PubMed

Kano, Taichi; Maruyama, Hiroki; Sakamoto, Ryu; Maruoka, Keiji

2015-06-21

In this communication, we present a regioselectivity switch for the chiral amine-catalysed asymmetric addition of aldehydes to reactive enals to afford either aldol adducts or conjugate adducts in a stereoselective fashion. The unprecedented asymmetric aldol reaction of aldehydes with enals was realized by the use of a diarylprolinol catalyst, giving synthetically useful and important chiral allylic alcohols.

Molecular Innovations Toward Theranostics of Aggressive Prostate Cancer

DTIC Science & Technology

2016-09-01

conjugation to drugs In preparation 4 Scope and limitations of ligation of peptides bearing an aldehyde or ketone group with dendrimers displaying...that triazinylhydrazine condense with the carbonyl groups of aldehydes and ketones . The intrinsic advantage of using a triazine comes with the...reacts efficiently with simple aldehydes and ketones , and with bioactives including the drug doxorubicin and bruceantin. Peptides bearing an N

Palladium-catalyzed, pyrrolidine-mediated arylmethylation of ketones and aldehydes with coumarinyl(methyl) acetates†

PubMed Central

Cattopadhyay, Kalicharan; Recio, Antonio; Tunge, Jon A.

2012-01-01

We report the palladium-catalyzed, pyrrolidine-mediated α-benzylation of enamines generated from aldehydes and ketones. The method allows for direct coupling of medicinally relevant coumarin moieties with aldehydes and ketones in good yield under mild conditions. The reaction is believed to proceed via a Pd-π-benzyl complex generated from (coumarinyl)methyl acetates. PMID:22832549

Expedient generation of patterned surface aldehydes by microfluidic oxidation for chemoselective immobilization of ligands and cells.

PubMed

Westcott, Nathan P; Pulsipher, Abigail; Lamb, Brian M; Yousaf, Muhammad N

2008-09-02

An expedient and inexpensive method to generate patterned aldehydes on self-assembled monolayers (SAMs) of alkanethiolates on gold with control of density for subsequent chemoselective immobilization from commercially available starting materials has been developed. Utilizing microfluidic cassettes, primary alcohol oxidation of tetra(ethylene glycol) undecane thiol and 11-mercapto-1-undecanol SAMs was performed directly on the surface generating patterned aldehyde groups with pyridinium chlorochromate. The precise density of surface aldehydes generated can be controlled and characterized by electrochemistry. For biological applications, fibroblast cells were seeded on patterned surfaces presenting biospecifc cell adhesive (Arg-Glyc-Asp) RGD peptides.

Results of Sediment Sampling and Elutriate Testing at the Proposed Wilson Island Shallow Water Habitat Project Site

DTIC Science & Technology

2013-08-01

Aroclor1248 0.3 1.0 Endrin 0.003 0.1 PCB - Aroclor1268 0.3 1.0 Endrin Aldehyde 0.011 0.1 PCB - Aroclor1232 0.2 1.0 Endrin Ketone 0.006 0.1 PCB...Endrin aldehyde ɛ ug/kg U EPA 8081 500 3 10 W1-E4 SEDIMENT Endrin aldehyde ɛ ug/kg U EPA 8081 500 3 10 W1-E1 NONFILTERED ELUTRIATE Endrin ketone ɘ.003...Endosulfan sulfate ----- 89 89 Endrin 0.086 0.036 ----- Endrin aldehyde ----- 0.30 0.30 Heptachlor 0.52 0.00079 0.00079 Heptachlor epoxide 0.52

Chemically Mediated Arrestment of the Bed Bug, Cimex lectularius, by Volatiles Associated with Exuviae of Conspecifics.

PubMed

Choe, Dong-Hwan; Park, Hoeun; Vo, Claudia; Knyshov, Alexander

2016-01-01

Extracts of the exuviae (cast skins) of nymphal bed bugs (Cimex lectularius) were analyzed for volatile compounds that might contribute to arrestment of adult bed bugs. Four volatile aldehydes, (E)-2-hexenal, 4-oxo-(E)-2-hexenal, (E)-2-octenal, and 4-oxo-(E)-2-octenal were consistently detected in the headspace of freshly shed exuviae regardless of the developmental stages from which the exuviae were obtained. Quantification of the aldehydes in the solvent extracts of homogenized fresh, 45- or 99-d aged 5th instar exuviae indicated that the aldehydes are present in the exuviae and dissipate over time, through evaporation or degradation. Microscopic observation of the fifth instar exuviae indicated that the dorsal abdominal glands on the exuviae maintained their pocket-like structures with gland reservoirs, within which the aldehydes might be retained. Two-choice olfactometer studies with the volatiles from exuviae or a synthetic blend mimicking the volatiles indicated that adult bed bugs tend to settle close to sources of the aldehydes. Our results imply that the presence and accumulation of bed bug exuviae and the aldehydes volatilizing from the exuviae might mediate bed bugs' interaction with their microhabitats.

Chemically Mediated Arrestment of the Bed Bug, Cimex lectularius, by Volatiles Associated with Exuviae of Conspecifics

PubMed Central

Choe, Dong-Hwan; Park, Hoeun; Vo, Claudia; Knyshov, Alexander

2016-01-01

Extracts of the exuviae (cast skins) of nymphal bed bugs (Cimex lectularius) were analyzed for volatile compounds that might contribute to arrestment of adult bed bugs. Four volatile aldehydes, (E)-2-hexenal, 4-oxo-(E)-2-hexenal, (E)-2-octenal, and 4-oxo-(E)-2-octenal were consistently detected in the headspace of freshly shed exuviae regardless of the developmental stages from which the exuviae were obtained. Quantification of the aldehydes in the solvent extracts of homogenized fresh, 45- or 99-d aged 5th instar exuviae indicated that the aldehydes are present in the exuviae and dissipate over time, through evaporation or degradation. Microscopic observation of the fifth instar exuviae indicated that the dorsal abdominal glands on the exuviae maintained their pocket-like structures with gland reservoirs, within which the aldehydes might be retained. Two-choice olfactometer studies with the volatiles from exuviae or a synthetic blend mimicking the volatiles indicated that adult bed bugs tend to settle close to sources of the aldehydes. Our results imply that the presence and accumulation of bed bug exuviae and the aldehydes volatilizing from the exuviae might mediate bed bugs’ interaction with their microhabitats. PMID:27434044

Brown Carbon Production in Aldehyde + Ammonium Sulfate Mixtures: Effects of Formaldehyde and Amines

NASA Astrophysics Data System (ADS)

Powelson, M.; De Haan, D. O.

2012-12-01

The formation of light-absorbing 'brown carbon,' or HULIS (humic- like substances), in atmospheric aerosol has an important impact on climate. However, the precursors responsible for brown carbon formation have not been identified. Several aldehydes present in clouds (methylglyoxal, glycolaldehyde, hydroxyacetone, glyoxal, and acetaldehyde) have the potential to create brown products when reacted with ammonium sulfate or primary amines such as methylamine or glycine. The formation of light-absorbing products from these reactions was characterized as a function of cloud-relevant pH (from 3- 6) using UV-Visible spectroscopy. Of the different aldehydes teste, the largest production rates of light-absorbing compounds were observed in reactions of glycolaldehyde and methylglyoxal. Primary amines produced more light- absorbing products than ammonium sulfate at lower concentrations. The addition of formaldehyde to any reaction with other aldehydes decreased the formation of light-absorbing products, while the addition of a small amount (1:5 mole ratio) of glycine to aldehyde + ammonium sulfate reactions can increase the production of light-absorbing products. These results suggest that the presence of primary amines significantly influence atmospheric brown carbon production by aldehydes even when much greater quantities of ammonium sulfate are present.

ALD5, PAD1, ATF1 and ATF2 facilitate the catabolism of coniferyl aldehyde, ferulic acid and p-coumaric acid in Saccharomyces cerevisiae

PubMed Central

Adeboye, Peter Temitope; Bettiga, Maurizio; Olsson, Lisbeth

2017-01-01

The ability of Saccharomyces cerevisiae to catabolize phenolic compounds remains to be fully elucidated. Conversion of coniferyl aldehyde, ferulic acid and p-coumaric acid by S. cerevisiae under aerobic conditions was previously reported. A conversion pathway was also proposed. In the present study, possible enzymes involved in the reported conversion were investigated. Aldehyde dehydrogenase Ald5, phenylacrylic acid decarboxylase Pad1, and alcohol acetyltransferases Atf1 and Atf2, were hypothesised to be involved. Corresponding genes for the four enzymes were overexpressed in a S. cerevisiae strain named APT_1. The ability of APT_1 to tolerate and convert the three phenolic compounds was tested. APT_1 was also compared to strains B_CALD heterologously expressing coniferyl aldehyde dehydrogenase from Pseudomonas, and an ald5Δ strain, all previously reported. APT_1 exhibited the fastest conversion of coniferyl aldehyde, ferulic acid and p-coumaric acid. Using the intermediates and conversion products of each compound, the catabolic route of coniferyl aldehyde, ferulic acid and p-coumaric acid in S. cerevisiae was studied in greater detail. PMID:28205618

Charged tag founded in N-(1-chloroalkyl)pyridinium quaternization for quantification of fatty aldehydes.

PubMed

Cao, Yanjing; Guan, Qing; Sun, Tuanqi; Qi, Wanshu; Guo, Yinlong

2016-09-21

N-(1-chloroalkyl)pyridinium quaternization was developed for the derivatization of fatty aldehydes. Differing from common pre-charged reagents, non-charged pyridine and thionyl chloride were designed to add permanently charged tag on aldehydes. Pyridine was far less competitive than charged derivatives in ionization. Thionyl chloride in excess was quenched by deionized water, converting into less residual sulfur dioxide bubbles. Thus solutions could be tested directly by mass spectrometry without further post-treatments. Pyridine-d5 labeled fatty aldehydes were prepared as internal standards. Mixed derivatives were then analyzed by high performance liquid chromatography coupled to positive electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Analytical parameters including reaction yield, stability, precision, linearity, and detection limits (LODs < 0.3 pg mL(-1)) were carefully validated. This method facilitated the analysis low content (ng mL(-1)) levels of free aliphatic aldehydes (C6C18) in human thyroid carcinoma and para-carcinoma tissue with a simple pretreatment procedure. Content of long chain nonvolatile aldehydes (C10C18) remarkably increased in thyroid carcinoma tissues (p < 0.05). Copyright © 2016. Published by Elsevier B.V.

Mechanisms of aldehyde-induced adenosinetriphosphatase activities of kinases.

PubMed

Rendina, A R; Cleland, W W

1984-10-23

Aldehyde analogues of the normal alcohol substrates induce ATPase activities by glycerokinase (D-glyceraldehyde), fructose-6-phosphate kinase (2,5-anhydromannose 6-phosphate), fructokinase (2,5-anhydromannose or 2,5-anhydrotalose), hexokinase (D-gluco-hexodialdose), choline kinase (betaine aldehyde), and pyruvate kinase (glyoxylate). Since purified deuterated aldehydes give V and V/K isotope effects near 1.0 for glycerokinase, fructokinase with 2,5-anhydro[1-2H]talose, hexokinase, choline kinase, and pyruvate kinase, the hydrates of these almost fully hydrated aldehydes are the activators of the ATPase reactions. Fructose-6-phosphate kinase and fructokinase with 2,5-anhydro[1-2H]mannose show V/K deuterium isotope effects of 1.10 and 1.22, respectively, suggesting either that both hydrate and free aldehyde may be activators (predicted values are 1.37 if only the free aldehyde activates the ATPase) or, more likely, that the phosphorylated hydrate breaks down in a rate-limiting step on the enzyme while MgADP is still present and the back-reaction to yield free hydrate in solution is still possible. 18O was transferred from the aldehyde hydrate to phosphate during the ATPase reactions of glycerokinase, fructose-6-phosphate kinase, fructokinase, and hexokinase but not with choline kinase or pyruvate kinase. Thus, direct phosphorylation of the hydrates by the first four enzymes gives the phosphate adduct of the aldehyde, which decomposes nonenzymatically, while with choline kinase and pyruvate kinase the hydrates induce transfer to water (metal-bound hydroxide or water with pyruvate kinase on the basis of pH profiles). Observation of a lag in the release of phosphate from the glycerokinase ATPase reaction at 15 degrees C supports the existence of a phosphorylated hydrate intermediate with a rate constant for breakdown of 0.035-0.043 s-1 at this temperature. Kinases that phosphorylate creatine, 3-phosphoglycerate, and acetate did not exhibit ATPase activities in the presence of keto or aldehyde analogues (N-methylhydantoic acid, D-glyceraldehyde 3-phosphate, and acetaldehyde, respectively), possibly because of the absence of an acid-base catalytic group in the latter two cases. These analogues were competitive inhibitors vs. the normal substrates, and in the latter case, the hydrate of acetaldehyde was shown to be the inhibitory species on the basis of the deuterium isotope effect on the inhibition constant.

Triggering the approach of an arene or heteroarene towards an aldehyde via Lewis acid-aldehyde communication.

PubMed

Pratihar, Sanjay

2016-03-14

The present work reports a combined experimental/computational study of the Lewis acid promoted hydroxyalkylation reaction involving aldehyde and arene/heteroarene and reveals a mechanism in which the rate determining aldehyde to alcohol formation via a four-member cyclic transition state (TS) involves a transfer of hydrogen from arene/heteroarene C-H to aldehyde oxygen with the breaking of the C-H bond and formation of C-C and O-H bonds. The effect of different Sn(iv) derivatives on the hydroxyalkylation reaction from different in situ NMR and computational studies reveals that although the exergonic formation of the intermediate and its gained electrophilicity at the carbonyl carbon drive the reaction in SnCl4 compared to other Sn(iv) derivatives, the overall reaction is low yielding because of its stable intermediate. With respect to different aldehydes, LA promoted hydroxylation was found to be more feasible for an electron withdrawing aldehyde compared to electron rich aldehyde because of lower stability, enhanced electrophilicity gained at the aldehyde center, and a lower activation barrier between its intermediate and TS in the former as compared to the latter. The relative stability of the LA-aldehyde adduct decreases in the order SnCl4 > AlCl3 > InCl3 > BF3 > ZnCl2 > TiCl4 > SiCl4, while the activation barrier (ΔG(#)) between intermediate and transition states increases in the order AlCl3 < SnCl4 < InCl3 < BF3 < TiCl4 < ZnCl2 < SiCl4. On the other hand, the activation barriers in the case of different arenes/heteroarenes are in the order of indole < furan < anisole < thiophene < toluene < benzene < chlorobenzene < cyanobenzene, which suggests a facile reaction in the case of indole and the most difficult reaction in the case of cyanobenzene. The ease of formation of the corresponding diaryl methyl carbocation from the alcohol-LA intermediate is responsible for the determination of the undesired product and is found to be more viable in the case of strong LAs like AlCl3, InCl3 and SnCl4 because they have negative free energy of formation (ΔG) for alcohol to the corresponding diaryl methyl carbocation.

A single inhalation exposure to acrolein desensitizes baroreflex responsiveness in Wistar-Kyoto and Spontaneously Hypertensive rats.

EPA Science Inventory

Arterial baroreflex is one of the body's homeostatic mechanisms that regulate blood pressure (BP) by changing heart rate (HR) and vasoconstriction. Increases in BP reflexively cause HR to decrease, whereas decreases in BP depress the baroreflex and cause HR to rise. As such, baro...

THE OZONE REACTION WITH BUTADIENE: FORMATION OF TOXIC PRODUCTS. (R826236)

EPA Science Inventory

Abstract

The formation yields of acrolein, 1,2-epoxy-3-butene and OH radicals have been measured from reaction of ozone with 1,3-butadiene at room temperature and atmosphere pressure. 1,3,5-Trimethyl benzene was added to scavenge OH radicals in measurements of product ...

EPA/Federal Highway Administration (FHWA) Near Road Collaboration Project: Las Vegas Near Road Study – MSAT Results

EPA Science Inventory

The series of studies conducted as part of the National Near Road Study focused on the collection of criteria air pollutants and mobile source air toxics (MSATs). The six priority compounds of interest were diesel particulate matter, benzene, 1,3-butadiene, acrolein, acetaldehyde...

Acrolein-Induced Increases in Blood Pressure and Heart Rate Are Coupled with Decreased Blood Oxygen Levels During Exposure in Hypertensive Rats

EPA Science Inventory

Exposure to air pollution increases the risk of cardiovascular morbidity and mortality, especially in individuals with pre-existing cardiovascular disease. Recent studies link exposure to air pollution with reduced blood oxygen saturation suggesting that hypoxia is a potential me...

40 CFR Table 2 to Subpart Jj of... - List of Volatile Hazardous Air Pollutants

Code of Federal Regulations, 2011 CFR

2011-07-01

...-Cresol 95487 m-Cresol 108394 p-Cresol 106445 Cumene 98828 2,4-D (2,4-Dichlorophenoxyacetic acid, including salts and esters) 94757 DDE (1,1-Dichloro-2,2-bis(p-chlorophenyl)ethylene) 72559 Diazomethane... 53963 Acrolein 107028 Acrylamide 79061 Acrylic acid 79107 Acrylonitrile 107131 Allyl chloride 107051 4...

21 CFR 176.300 - Slimicides.

Code of Federal Regulations, 2010 CFR

2010-04-01

... provided for under paragraph (d) of this section. (3) Slimicides are added to the process water used in the... substances Limitations Acrolein Alkenyl (C16-C18) dimethylethyl-ammonium bromide n-Alkyl (C12-C18) dimethyl benzyl ammonium chloride 1,2-Benzisothiazolin-3-one At a level of 0.06 pound per ton of dry weight fiber...

NIOSH Manual of Analytical Methods (third edition). Fourth supplement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1990-08-15

The NIOSH Manual of Analytical Methods, 3rd edition, was updated for the following chemicals: allyl-glycidyl-ether, 2-aminopyridine, aspartame, bromine, chlorine, n-butylamine, n-butyl-glycidyl-ether, carbon-dioxide, carbon-monoxide, chlorinated-camphene, chloroacetaldehyde, p-chlorophenol, crotonaldehyde, 1,1-dimethylhydrazine, dinitro-o-cresol, ethyl-acetate, ethyl-formate, ethylenimine, sodium-fluoride, hydrogen-fluoride, cryolite, sodium-hexafluoroaluminate, formic-acid, hexachlorobutadiene, hydrogen-cyanide, hydrogen-sulfide, isopropyl-acetate, isopropyl-ether, isopropyl-glycidyl-ether, lead, lead-oxide, maleic-anhydride, methyl-acetate, methyl-acrylate, methyl-tert-butyl ether, methyl-cellosolve-acetate, methylcyclohexanol, 4,4'-methylenedianiline, monomethylaniline, monomethylhydrazine, nitric-oxide, p-nitroaniline, phenyl-ether, phenyl-ether-biphenyl mixture, phenyl-glycidyl-ether, phenylhydrazine, phosphine, ronnel, sulfuryl-fluoride, talc, tributyl-phosphate, 1,1,2-trichloro-1,2,2-trifluoroethane, trimellitic-anhydride, triorthocresyl-phosphate, triphenyl-phosphate, and vinyl-acetate.

Effect of Water on Ethanol Conversion over ZnO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rahman, Muhammad Mahfuzur; Davidson, Stephen D.; Sun, Junming

2015-10-01

This work focuses on understanding the role of water on ethanol conversion over zinc oxide (ZnO). It was found that a competitive adsorption between ethanol and water occurs on ZnO, which leads to the blockage of the strong Lewis acid site by water on ZnO. As a result, both dehydration and dehydrogenation reactions are inhibited. However, the extent of inhibition for dehydration is orders of magnitude higher than that for dehydrogenation, leading to the shift of reaction pathway from ethanol dehydration to dehydrogenation. In the secondary reactions for acetaldehyde conversion, water inhibits the acetaldehyde aldol-condensation to crotonaldehyde, favoring the oxidationmore » of acetaldehyde to acetic acid, and then to acetone via ketonization at high temperature (i.e., 400 °C).« less

Environmental Electrophiles: Protein Adducts, Modulation of Redox Signaling, and Interaction with Persulfides/Polysulfides.

PubMed

Kumagai, Yoshito; Abiko, Yumi

2017-01-17

Included among the many environmental electrophiles are aromatic hydrocarbon quinones formed during combustion of gasoline, crotonaldehyde in tobacco smoke, methylmercury accumulated in fish, cadmium contaminated in rice, and acrylamide in baked foods. These electrophiles can modify nucleophilic functions such as cysteine residues in proteins forming adducts and in the process activate cellular redox signal transduction pathways such as kinases and transcription factors. However, higher concentrations of electrophiles disrupt such signaling by nonselective covalent modification of cellular proteins. Persulfide/polysulfides produced by various enzymes appear to capture environmental electrophiles because of the formation of their sulfur adducts without electrophilicity. We therefore speculate that persulfide/polysulfides are candidates for the regulation of redox signal transduction pathways (e.g., cell survival, cell proliferation, and adaptive response) and toxicity during exposure to environmental electrophiles.

Accurate determination of aldehydes in amine catalysts or amines by 2,4-dinitrophenylhydrazine derivatization.

PubMed

Barman, Bhajendra N

2014-01-31

Carbonyl compounds, specifically aldehydes, present in amine catalysts or amines are determined by reversed-phase liquid chromatography using ultraviolet detection of their corresponding 2,4-dinitrophenylhydrazones. The primary focus has been to establish optimum conditions for determining aldehydes accurately because these add exposure concerns when the amine catalysts are used to manufacture polyurethane products. Concentrations of aldehydes determined by this method are found to vary with the pH of the aqueous amine solution and the derivatization time, the latter being problematic when the derivatization reaction proceeds slowly and not to completion in neutral and basic media. Accurate determination of aldehydes in amines through derivatization can be carried out at an effective solution pH of about 2 and with derivatization time of 20min. Hydrochloric acid has been used for neutralization of an amine. For complete derivatization, it is essential to protonate all nitrogen atoms in the amine. An approach for the determination of an adequate amount of acid needed for complete derivatization has been described. Several 0.2M buffer solutions varying in pH from 4 to 8 have also been used to make amine solutions for carrying out derivatization of aldehydes. These solutions have effective pHs of 10 or higher and provide much lower aldehyde concentrations compared to their true values. Mechanisms for the formation of 2,4-dinitrophenylhydrazones in both acidic and basic media are discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

Transcription factor Nrf2 mediates an adaptive response to sulforaphane that protects fibroblasts in vitro against the cytotoxic effects of electrophiles, peroxides and redox-cycling agents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Higgins, Larry G.; Kelleher, Michael O.; Eggleston, Ian M.

2009-06-15

Sulforaphane can stimulate cellular adaptation to redox stressors through transcription factor Nrf2. Using mouse embryonic fibroblasts (MEFs) as a model, we show herein that the normal homeostatic level of glutathione in Nrf2{sup -/-} MEFs was only 20% of that in their wild-type counterparts. Furthermore, the rate of glutathione synthesis following its acute depletion upon treatment with 3 {mu}mol/l sulforaphane was very substantially lower in Nrf2{sup -/-} MEFs than in wild-type cells, and the rebound leading to a {approx} 1.9-fold increase in glutathione that occurred 12-24 h after Nrf2{sup +/+} MEFs were treated with sulforaphane was not observed in Nrf2{sup -/-}more » fibroblasts. Wild-type MEFs that had been pre-treated for 24 h with 3 {mu}mol/l sulforaphane exhibited between 1.4- and 3.2-fold resistance against thiol-reactive electrophiles, including isothiocyanates, {alpha},{beta}-unsaturated carbonyl compounds (e.g. acrolein), aryl halides and alkene epoxides. Pre-treatment of Nrf2{sup +/+} MEFs with sulforaphane also protected against hydroperoxides (e.g. cumene hydroperoxide, CuOOH), free radical-generating compounds (e.g. menadione), and genotoxic electrophiles (e.g. chlorambucil). By contrast, Nrf2{sup -/-} MEFs were typically {approx} 50% less tolerant of these agents than wild-type fibroblasts, and sulforaphane pre-treatment did not protect the mutant cells against xenobiotics. To test whether Nrf2-mediated up-regulation of glutathione represents the major cytoprotective mechanism stimulated by sulforaphane, 5 {mu}mol/l buthionine sulfoximine (BSO) was used to inhibit glutathione synthesis. In Nrf2{sup +/+} MEFs pre-treated with sulforaphane, BSO diminished intrinsic resistance and abolished inducible resistance to acrolein, CuOOH and chlorambucil, but not menadione. Thus Nrf2-dependent up-regulation of GSH is the principal mechanism by which sulforaphane pre-treatment induced resistance to acrolein, CuOOH and chlorambucil, but not menadione.« less

Menthol attenuates respiratory irritation and elevates blood cotinine in cigarette smoke exposed mice.

PubMed

Ha, Michael A; Smith, Gregory J; Cichocki, Joseph A; Fan, Lu; Liu, Yi-Shiuan; Caceres, Ana I; Jordt, Sven Eric; Morris, John B

2015-01-01

Addition of menthol to cigarettes may be associated with increased initiation of smoking. The potential mechanisms underlying this association are not known. Menthol, likely due to its effects on cold-sensing peripheral sensory neurons, is known to inhibit the sensation of irritation elicited by respiratory irritants. However, it remains unclear whether menthol modulates cigarette smoke irritancy and nicotine absorption during initial exposures to cigarettes, thereby facilitating smoking initiation. Using plethysmography in a C57Bl/6J mouse model, we examined the effects of L-menthol, the menthol isomer added to cigarettes, on the respiratory sensory irritation response to primary smoke irritants (acrolein and cyclohexanone) and smoke of Kentucky reference 2R4 cigarettes. We also studied L-menthol's effect on blood levels of the nicotine metabolite, cotinine, immediately after exposure to cigarette smoke. L-menthol suppressed the irritation response to acrolein with an apparent IC₅₀ of 4 ppm. Suppression was observed even at acrolein levels well above those necessary to produce a maximal response. Cigarette smoke, at exposure levels of 10 mg/m³ or higher, caused an immediate and marked sensory irritation response in mice. This response was significantly suppressed by L-menthol even at smoke concentrations as high as 300 mg/m³. Counterirritation by L-menthol was abolished by treatment with a selective inhibitor of Transient Receptor Potential Melastatin 8 (TRPM8), the neuronal cold/menthol receptor. Inclusion of menthol in the cigarette smoke resulted in roughly a 1.5-fold increase in plasma cotinine levels over those observed in mice exposed to smoke without added menthol. These findings document that, L-menthol, through TRPM8, is a strong suppressor of respiratory irritation responses, even during highly noxious exposures to cigarette smoke or smoke irritants, and increases blood cotinine. Therefore, L-menthol, as a cigarette additive, may promote smoking initiation and nicotine addiction.

Chronic adriamycin treatment impairs CGRP-mediated functions of meningeal sensory nerves.

PubMed

Deák, Éva; Rosta, Judit; Boros, Krisztina; Kis, Gyöngyi; Sántha, Péter; Messlinger, Karl; Jancsó, Gábor; Dux, Mária

2018-06-01

Adriamycin is a potent anthracycline-type antitumor agent, but it also exerts potentially serious side effects due to its cardiotoxic and neurotoxic propensity. Multiple impairments in sensory nerve functions have been recently reported in various rat models. The present experiments were initiated in an attempt to reveal adriamycin-induced changes in sensory effector functions of chemosensitive meningeal afferents. Meningeal blood flow was measured with laser Doppler flowmetry in the parietal dura mater of adult male Wistar rats. The dura mater was repeatedly stimulated by topical applications of capsaicin, a transient receptor potential vanilloid 1 (TRPV1) receptor agonist, or acrolein, a transient receptor potential ankyrin 1 (TRPA1) receptor agonist, which induce the release of calcitonin gene-related peptide (CGRP) from meningeal afferents. The blood flow increasing effects of CGRP, histamine, acetylcholine and forskolin were also measured. Capsaicin- and acrolein-induced CGRP release was measured with enzyme-linked immunoassay in an ex vivo dura mater preparation. TRPV1 content of trigeminal ganglia and TRPV1-, CGRP- and CGRP receptor component-immunoreactive structures were examined in dura mater samples obtained from control and adriamycin-treated rats. The vasodilator effects of capsaicin, acrolein and CGRP were significantly reduced in adriamycin-treated animals while histamine-, acetylcholine- and forskolin-induced vasodilatation were unaffected. Measurements of CGRP release in an ex vivo dura mater preparation revealed an altered dynamic upon repeated stimulations of TRPV1 and TRPA1 receptors. In whole-mount dura mater preparations immunohistochemistry revealed altered CGRP receptor component protein (RCP)-immunoreactivity in adriamycin-treated animals, while CGRP receptor activity modifying protein (RAMP1)-, TRPV1- and CGRP-immunostaining were left apparently unaltered. Adriamycin-treatment slightly reduced TRPV1 protein content of trigeminal ganglia. The present findings demonstrate that adriamycin-treatment alters the function of the trigeminovascular system leading to reduced meningeal sensory neurogenic vasodilatation that may affect the local regulatory and protective mechanisms of chemosensitive afferents leading to alterations in tissue integrity. Copyright © 2018 Elsevier Ltd. All rights reserved.

Dermal carbonyl modification is related to the yellowish color change of photo-aged Japanese facial skin.

PubMed

Ogura, Yuki; Kuwahara, Tomohiro; Akiyama, Minoru; Tajima, Shingo; Hattori, Kazuhisa; Okamoto, Kouhei; Okawa, Shinpei; Yamada, Yukio; Tagami, Hachiro; Takahashi, Motoji; Hirao, Tetsuji

2011-10-01

The photo-aged facial skin is characterized by various unique features such as dark spots, wrinkles, and sagging. Elderly people, particularly Asians, tend to show a yellowish skin color change with photo-aging. However, there has been no analytical study conducted on this unique skin color change of the aged facial skin. The purpose of the present study is to examine whether the carbonyl modification in the dermal protein is involved in the yellowish color change that occurs in the photo-aged skin. Normal skin samples excised from the face, abdomen and buttock of variously aged Japanese were separated into the epidermal and the dermal portions. These skin samples were histologically examined for carbonyl modification. Moreover, an in vitro constructed dermis model composed of a contracted collagen gel was treated with acrolein or 4-hydroxynonenal. All these samples were also studied colorimetrically. The dermal samples obtained from the photo-aged facial skin exhibited an appearance of yellowish color, whereas neither the facial epidermis nor the dermis obtained from the abdomen or buttock showed such a yellowish discoloration. The upper layer of the dermis that revealed the yellowish color showed elastosis whose elastic fibers were found to colocalize with carbonyl protein as detected by a labeled hydrazide, as well as by an immunohistochemical examination using the antibody against acrolein adduct. Experimental induction of carbonyl modification in a dermis model in vitro by a long-term treatment with acrolein or 4-hydroxynonenal was found to show the appearance of the yellowish change which was also proven by an increase in b* value of colorimetry. It was more pronounced than that induced by glycation. Our present results strongly suggest that carbonyl modification of the dermal protein is involved in the production of the yellowish color change that is noted in the photo-aged facial skin. Copyright © 2011 Japanese Society for Investigative Dermatology. Published by Elsevier Ireland Ltd. All rights reserved.

Children's exposure to secondhand and thirdhand smoke carcinogens and toxicants in homes of hookah smokers.

PubMed

Kassem, Nada O F; Daffa, Reem M; Liles, Sandy; Jackson, Sheila R; Kassem, Noura O; Younis, Maram A; Mehta, Setoo; Chen, Menglan; Jacob, Peyton; Carmella, Steve G; Chatfield, Dale A; Benowitz, Neal L; Matt, Georg E; Hecht, Stephen S; Hovell, Melbourne F

2014-07-01

We examined homes of hookah-only smokers and nonsmokers for levels of indoor air nicotine (a marker of secondhand smoke) and indoor surface nicotine (a marker of thirdhand smoke), child uptake of nicotine, the carcinogen 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), and the toxicant acrolein by analyzing their corresponding metabolites cotinine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) and NNAL-glucuronides (total NNAL) and 3-hydroxypropylmercapturic acid. Data were collected at 3 home visits during a 7-day study period from a convenience sample of 24 households with a child 5 years or younger. Three child urine samples and 2 air and surface samples from the living room and the child bedroom were taken in homes of nonsmokers (n = 5) and hookah-only smokers (n = 19) comprised of daily hookah smokers (n = 8) and weekly/monthly hookah smokers (n = 11). Nicotine levels in indoor air and on surfaces in the child bedrooms in homes of daily hookah smokers were significantly higher than in homes of nonsmokers. Uptake of nicotine, NNK, and acrolein in children living in daily hookah smoker homes was significantly higher than in children living in nonsmoker homes. Uptake of nicotine and NNK in children living in weekly/monthly hookah smoker homes was significantly higher than in children living in nonsmoker homes. Our data provide the first evidence for uptake of nicotine, the tobacco-specific lung carcinogen NNK, and the ciliatoxic and cardiotoxic agent acrolein in children living in homes of hookah smokers. Our findings suggest that daily and occasional hookah use in homes present a serious, emerging threat to children's long-term health. © The Author 2014. Published by Oxford University Press on behalf of the Society for Research on Nicotine and Tobacco. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Menthol Attenuates Respiratory Irritation and Elevates Blood Cotinine in Cigarette Smoke Exposed Mice

PubMed Central

Ha, Michael A.; Smith, Gregory J.; Cichocki, Joseph A.; Fan, Lu; Liu, Yi-Shiuan; Caceres, Ana I.; Jordt, Sven Eric; Morris, John B.

2015-01-01

Addition of menthol to cigarettes may be associated with increased initiation of smoking. The potential mechanisms underlying this association are not known. Menthol, likely due to its effects on cold-sensing peripheral sensory neurons, is known to inhibit the sensation of irritation elicited by respiratory irritants. However, it remains unclear whether menthol modulates cigarette smoke irritancy and nicotine absorption during initial exposures to cigarettes, thereby facilitating smoking initiation. Using plethysmography in a C57Bl/6J mouse model, we examined the effects of L-menthol, the menthol isomer added to cigarettes, on the respiratory sensory irritation response to primary smoke irritants (acrolein and cyclohexanone) and smoke of Kentucky reference 2R4 cigarettes. We also studied L-menthol’s effect on blood levels of the nicotine metabolite, cotinine, immediately after exposure to cigarette smoke. L-menthol suppressed the irritation response to acrolein with an apparent IC₅₀ of 4 ppm. Suppression was observed even at acrolein levels well above those necessary to produce a maximal response. Cigarette smoke, at exposure levels of 10 mg/m³ or higher, caused an immediate and marked sensory irritation response in mice. This response was significantly suppressed by L-menthol even at smoke concentrations as high as 300 mg/m³. Counterirritation by L-menthol was abolished by treatment with a selective inhibitor of Transient Receptor Potential Melastatin 8 (TRPM8), the neuronal cold/menthol receptor. Inclusion of menthol in the cigarette smoke resulted in roughly a 1.5-fold increase in plasma cotinine levels over those observed in mice exposed to smoke without added menthol. These findings document that, L-menthol, through TRPM8, is a strong suppressor of respiratory irritation responses, even during highly noxious exposures to cigarette smoke or smoke irritants, and increases blood cotinine. Therefore, L-menthol, as a cigarette additive, may promote smoking initiation and nicotine addiction. PMID:25679525

Metal-free one-pot oxidative amination of aldehydes to amides.

PubMed

Ekoue-Kovi, Kekeli; Wolf, Christian

2007-08-16

Metal-free oxidative amination of aromatic aldehydes in the presence of TBHP provides convenient access to amides in 85-99% under mild reaction conditions within 5 h. This method avoids free carboxylic acid intermediates and integrates aldehyde oxidation and amide bond formation, which are usually accomplished separately, into a single operation. Proline-derived amides can be prepared in excellent yields without noticeable racemization.

Knölker's iron complex: an efficient in situ generated catalyst for reductive amination of alkyl aldehydes and amines.

PubMed

Pagnoux-Ozherelyeva, Anastassiya; Pannetier, Nicolas; Mbaye, Mbaye Diagne; Gaillard, Sylvain; Renaud, Jean-Luc

2012-05-14

An aminated series: a well-defined iron-catalyzed reductive amination reaction of aldehydes and ketones with aliphatic amines using molecular hydrogen is presented. Under mild conditions, good yields for a broad range of alkyl ketones as well as aldehydes were achieved. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formaldehyde Five-Day Passive Chemical Dosimeter Badge Validation Study

DTIC Science & Technology

2012-11-30

of organic carbonyl compounds ( aldehydes and ketones ) with DNPH-coated silica gel badges/cartridges in the presence of a strong acid, as a catalyst...more stringent 90-day limit of 100ppb is imminent.2 Experimental Materials Aldehyde badges (#571) were obtained from Assay Technology...Inc., Livermore, CA. This badge collects aldehydes on a glass fiber filter treated with acidified 2,4- dinitrophenylhydrazine (DNPH.) Standard field

Small Molecule Protection of Bone Marrow Hematopoietic Stem Cells

DTIC Science & Technology

2015-10-01

several recently identified small molecules can protect hematopoietic stem cells (HSCs) from damage or killing by endogenous aldehydes . Proof-of-concept...anemia bone marrow failure CD34+ hematopoietic stem cells aldehydes formaldehyde DNA damage DNA base adduct DNA-protein crosslink mass...below. Revised Specific Aim 1: Small molecule protection of human cells from aldehyde - induced killing (in vitro studies - no mice or human subjects

A rapid and efficient one-pot method for the reduction of N-protected α-amino acids to chiral α-amino aldehydes using CDI/DIBAL-H.

PubMed

Ivkovic, Jakov; Lembacher-Fadum, Christian; Breinbauer, Rolf

2015-11-14

N-Protected amino acids can be easily converted into chiral α-amino aldehydes in a one-pot reaction by activation with CDI followed by reduction with DIBAL-H. This method delivers Boc-, Cbz- and Fmoc-protected amino aldehydes from proteinogenic amino acids in very good isolated yields and complete stereointegrity.

Process for producing peracids from aliphatic hydroxy carboxylic acids

DOEpatents

Chum, Helena L.; Ratcliff, Matthew A.; Palasz, Peter D.

1986-01-01

A process for producing peracids from lactic acid-containing solutions derived from biomass processing systems comprising: adjusting the pH of the solution to about 8-9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids; oxidizing the solution to produce volatile lower aliphatic aldehydes; removing said aldehydes as they are generated; and converting said aldehydes to peracids.

Synthesis of β-C-Glycopyranosyl Aldehydes and 2,6-Anhydro-heptitols.

PubMed

Khatri, Vinod; Kumar, Amit; Singh, Balram; Malhotra, Shashwat; Prasad, Ashok K

2015-11-06

A convenient route has been developed for the diastereoselective synthesis of β-C-glycopyranosyl aldehydes from D-glucose, D-mannose, and D-galactose. The key step in the synthesis of C-glycosyl aldehydes is the aryl driven reductive dehydration on 1-phenyl-2-(2',3',4',6'-tetra-O-acetyl-β-D-glycopyranosyl)ethanone to afford alkenes, which on oxidation afford the desired compounds in good yield. β-C-Glycopyranosyl aldehydes have been converted to 2,6-anhydro-heptitols in quantitative yields. The 2,6-anhydro-heptitols derived from D-mannose and D-galactose are enantiomeric and are useful linkers for the synthesis of macrocycles/amphiphiles of complementary chirality.

Structural and functional analysis of betaine aldehyde dehydrogenase from Staphylococcus aureus.

PubMed

Halavaty, Andrei S; Rich, Rebecca L; Chen, Chao; Joo, Jeong Chan; Minasov, George; Dubrovska, Ievgeniia; Winsor, James R; Myszka, David G; Duban, Mark; Shuvalova, Ludmilla; Yakunin, Alexander F; Anderson, Wayne F

2015-05-01

When exposed to high osmolarity, methicillin-resistant Staphylococcus aureus (MRSA) restores its growth and establishes a new steady state by accumulating the osmoprotectant metabolite betaine. Effective osmoregulation has also been implicated in the acquirement of a profound antibiotic resistance by MRSA. Betaine can be obtained from the bacterial habitat or produced intracellularly from choline via the toxic betaine aldehyde (BA) employing the choline dehydrogenase and betaine aldehyde dehydrogenase (BADH) enzymes. Here, it is shown that the putative betaine aldehyde dehydrogenase SACOL2628 from the early MRSA isolate COL (SaBADH) utilizes betaine aldehyde as the primary substrate and nicotinamide adenine dinucleotide (NAD(+)) as the cofactor. Surface plasmon resonance experiments revealed that the affinity of NAD(+), NADH and BA for SaBADH is affected by temperature, pH and buffer composition. Five crystal structures of the wild type and three structures of the Gly234Ser mutant of SaBADH in the apo and holo forms provide details of the molecular mechanisms of activity and substrate specificity/inhibition of this enzyme.

Direct, enantioselective α-alkylation of aldehydes using simple olefins.

PubMed

Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

Asymmetric intramolecular α-cyclopropanation of aldehydes using a donor/acceptor carbene mimetic

PubMed Central

Luo, Chaosheng; Wang, Zhen; Huang, Yong

2015-01-01

Enantioselective α-alkylation of carbonyl is considered as one of the most important processes for asymmetric synthesis. Common alkylation agents, that is, alkyl halides, are notorious substrates for both Lewis acids and organocatalysts. Recently, olefins emerged as a benign alkylating species via photo/radical mechanisms. However, examples of enantioselective alkylation of aldehydes/ketones are scarce and direct asymmetric dialkylation remains elusive. Here we report an intramolecular α-cyclopropanation reaction of olefinic aldehydes to form chiral cyclopropane aldehydes. We demonstrate that an α-iodo aldehyde can function as a donor/acceptor carbene equivalent, which engages in a formal [2+1] annulation with a tethered double bond. Privileged bicyclo[3.1.0]hexane-type scaffolds are prepared in good optical purity using a chiral amine. The synthetic utility of the products is demonstrated by versatile transformations of the bridgehead formyl functionality. We expect the concept of using α-iodo iminium as a donor/acceptor carbene surrogate will find wide applications in chemical reaction development. PMID:26644194

The First Mammalian Aldehyde Oxidase Crystal Structure

PubMed Central

Coelho, Catarina; Mahro, Martin; Trincão, José; Carvalho, Alexandra T. P.; Ramos, Maria João; Terao, Mineko; Garattini, Enrico; Leimkühler, Silke; Romão, Maria João

2012-01-01

Aldehyde oxidases (AOXs) are homodimeric proteins belonging to the xanthine oxidase family of molybdenum-containing enzymes. Each 150-kDa monomer contains a FAD redox cofactor, two spectroscopically distinct [2Fe-2S] clusters, and a molybdenum cofactor located within the protein active site. AOXs are characterized by broad range substrate specificity, oxidizing different aldehydes and aromatic N-heterocycles. Despite increasing recognition of its role in the metabolism of drugs and xenobiotics, the physiological function of the protein is still largely unknown. We have crystallized and solved the crystal structure of mouse liver aldehyde oxidase 3 to 2.9 Å. This is the first mammalian AOX whose structure has been solved. The structure provides important insights into the protein active center and further evidence on the catalytic differences characterizing AOX and xanthine oxidoreductase. The mouse liver aldehyde oxidase 3 three-dimensional structure combined with kinetic, mutagenesis data, molecular docking, and molecular dynamics studies make a decisive contribution to understand the molecular basis of its rather broad substrate specificity. PMID:23019336

Bioactivation to an aldehyde metabolite--possible role in the onset of toxicity induced by the anti-HIV drug abacavir.

PubMed

Grilo, Nádia M; Charneira, Catarina; Pereira, Sofia A; Monteiro, Emília C; Marques, M Matilde; Antunes, Alexandra M M

2014-01-30

Aldehydes are highly reactive molecules, which can be generated during numerous physiological processes, including the biotransformation of drugs. Several non-P450 enzymes participate in their metabolism albeit alcohol dehydrogenase and aldehyde dehydrogenase are the ones most frequently involved in this process. Endogenous and exogenous aldehydes have been strongly implicated in multiple human pathologies. Their ability to react with biomacromolecules (e.g. proteins) yielding covalent adducts is suggested to be the common primary mechanism underlying the toxicity of these reactive species. Abacavir is one of the options for combined anti-HIV therapy. Although individual susceptibilities to adverse effects differ among patients, abacavir is associated with idiosyncratic hypersensitivity drug reactions and an increased risk of cardiac dysfunction. This review highlights the current knowledge on abacavir metabolism and discusses the potential role of bioactivation to an aldehyde metabolite, capable of forming protein adducts, in the onset of abacavir-induced toxic outcomes. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Direct, enantioselective α-alkylation of aldehydes using simple olefins

PubMed Central

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-01-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons. PMID:29064486

Direct, enantioselective α-alkylation of aldehydes using simple olefins

NASA Astrophysics Data System (ADS)

Capacci, Andrew G.; Malinowski, Justin T.; McAlpine, Neil J.; Kuhne, Jerome; MacMillan, David W. C.

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes—photoredox, enamine and hydrogen-atom transfer (HAT) catalysis—enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

Carbon-Carbon Bond Formation and Hydrogen Production in the Ketonization of Aldehydes.

PubMed

Orozco, Lina M; Renz, Michael; Corma, Avelino

2016-09-08

Aldehydes possess relatively high chemical energy, which is the driving force for disproportionation reactions such as Cannizzaro and Tishchenko reactions. Generally, this energy is wasted if aldehydes are transformed into carboxylic acids with a sacrificial oxidant. Here, we describe a cascade reaction in which the surplus energy of the transformation is liberated as molecular hydrogen for the oxidation of heptanal to heptanoic acid by water, and the carboxylic acid is transformed into potentially industrially relevant symmetrical ketones by ketonic decarboxylation. The cascade reaction is catalyzed by monoclinic zirconium oxide (m-ZrO2 ). The reaction mechanism has been studied through cross-coupling experiments between different aldehydes and acids, and the final symmetrical ketones are formed by a reaction pathway that involves the previously formed carboxylic acids. Isotopic studies indicate that the carboxylic acid can be formed by a hydride shift from the adsorbed aldehyde on the metal oxide surface in the absence of noble metals. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methodology for in situ protection of aldehydes and ketones using trimethylsilyl trifluoromethanesulfonate and phosphines: selective alkylation and reduction of ketones, esters, amides, and nitriles.

PubMed

Yahata, Kenzo; Minami, Masaki; Yoshikawa, Yuki; Watanabe, Kei; Fujioka, Hiromichi

2013-01-01

A methodology for selective transformations of ketones, esters, Weinreb amides, and nitriles in the presence of aldehydes has been developed. The use of a combination of PPh(3)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) promotes selective transformation of aldehydes to their corresponding, temporarily protected, O,P-acetal type phosphonium salts. Because, hydrolytic work-up following ensuing reactions of other carbonyl moieties in the substrates liberates the aldehyde moiety, a sequence involving aldehyde protection, transformation of other carbonyl groups, and deprotection can be accomplished in a one-pot manner. Furthermore, the use of PEt(3) instead of PPh(3) enables ketones to be converted in situ to their corresponding O,P-ketal type phosphonium salts and, consequently, selective transformations of esters, Weinreb amides, and nitriles in the presence of ketones can be performed. This methodology is applicable to various dicarbonyl compounds, including substrates that possess heteroaromatic skeletons and hydroxyl protecting groups.

The color expression of copigmentation between malvidin-3-O-glucoside and three phenolic aldehydes in model solutions: The effects of pH and molar ratio.

PubMed

Zhang, Bo; He, Fei; Zhou, Pan-Pan; Liu, Yue; Duan, Chang-Qing

2016-05-15

Copigmentation was investigated in model solutions between the anthocyanin malvidin-3-O-glucoside and three phenolic aldehydes (vanillic, syringic and coniferyl aldehydes) as a function of the pH and the pigment/copigment molar ratio. Tristimulus colorimetry was applied to evaluate the chromatic variations induced by copigmentation process. The results indicated that the greatest magnitude of copigmentation was obtained at pH 3.0 and molar ratio of 1:100, being significantly higher with coniferyl aldehyde, followed by syringic and vanillic aldehydes. The equilibrium constant (K) and Gibbs free energies (ΔG°) determined here show a spontaneous exothermic reaction. Theoretical calculations (ΔGbinding, ΔE) specified the relative arrangement of the pigment and copigment molecules within the complexes. In addition, an atoms in molecules (AIM) analysis was used to explore the main driving forces contributing to the formation of copigmentation complexes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hollow-fiber liquid-phase microextraction coupled with miniature capillary electrophoresis for the trace analysis of four aliphatic aldehydes in water samples.

PubMed

Li, Ying; Yi, Fan; Zheng, Yiliang; Wang, Yu; Ye, Jiannong; Chu, Qingcui

2015-08-01

An environmentally friendly method for the trace analysis of four aliphatic aldehydes as water disinfection byproducts has been developed based on hollow-fiber liquid-phase microextraction followed by miniature capillary electrophoresis with amperometric detection. After derivatization with 2-thiobarbituric acid, four aliphatic aldehydes (formaldehyde, acetaldehyde, propylaldehyde, and butyraldehyde) became detectable by the amperometric detector. Under the optimum conditions, four aliphatic aldehydes can be well separated from the coexisting interferents as well as their homologs (pentanal, glyoxal, and methyl-glyoxal), and the limits of detection (S/N = 3) could reach sub-nanogram-per-milliliter level based on hollow-fiber liquid-phase microextraction. The proposed method has been applied for the analyses of above four aliphatic aldehydes in different water samples such as drinking water, tap water, and river water, and the average recoveries were in the range of 90-113%, providing an alternative to conventional and microchip capillary electrophoresis approaches. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.