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Sample records for acrolein formaldehyde methanol

  1. Acrolein

    PubMed Central

    Stevens, Jan F.; Maier, Claudia S.

    2008-01-01

    Acrolein (2-propenal) is ubiquitously present in (cooked) foods and in the environment. It is formed from carbohydrates, vegetable oils and animal fats, amino acids during heating of foods, and by combustion of petroleum fuels and biodiesel. Chemical reactions responsible for release of acrolein include heat-induced dehydration of glycerol, retro-aldol cleavage of dehydrated carbohydrates, lipid peroxidation of polyunsaturated fatty acids, and Strecker degradation of methionine and threonine. Smoking of tobacco products equals or exceeds the total human exposure to acrolein from all other sources. The main endogenous sources of acrolein are myeloperoxidase-mediated degradation of threonine and amine oxidase-mediated degradation of spermine and spermidine, which may constitute a significant source of acrolein in situations of oxidative stress and inflammation. Acrolein is metabolized by conjugation with glutathione and excreted in the urine as mercapturic acid metabolites. Acrolein forms Michael adducts with ascorbic acid in vitro, but the biological relevance of this reaction is not clear. The biological effects of acrolein are a consequence of its reactivity towards biological nucleophiles such as guanine in DNA and cysteine, lysine, histidine, and arginine residues in critical regions of nuclear factors, proteases, and other proteins. Acrolein adduction disrupts the function of these biomacromolecules which may result in mutations, altered gene transcription, and modulation of apoptosis. PMID:18203133

  2. Acrolein

    Integrated Risk Information System (IRIS)

    Acrolein ; CASRN 107 - 02 - 8 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 Effects

  3. Self-Sufficient Formaldehyde-to-Methanol Conversion by Organometallic Formaldehyde Dismutase Mimic.

    PubMed

    van der Waals, Dominic; Heim, Leo E; Vallazza, Simona; Gedig, Christian; Deska, Jan; Prechtl, Martin H G

    2016-08-01

    The catalytic networks of methylotrophic organisms, featuring redox enzymes for the activation of one-carbon moieties, can serve as great inspiration in the development of novel homogeneously catalyzed pathways for the interconversion of C1 molecules at ambient conditions. An imidazolium-tagged arene-ruthenium complex was identified as an effective functional mimic of the bacterial formaldehyde dismutase, which provides a new and highly selective route for the conversion of formaldehyde to methanol in absence of any external reducing agents. Moreover, secondary amines are reductively methylated by the organometallic dismutase mimic in a redox self-sufficient manner with formaldehyde acting both as carbon source and reducing agent.

  4. Formaldehyde-methanol, metallic-oxide agents head scavengers list

    SciTech Connect

    Schaack, J.P.; Chan, F.

    1989-01-23

    Use of batch-operated chemical H/sub 2/S scavengers as an inexpensive gas-sweetening process may be an attractive alternative for moderately sour gas wells with small production remote from a gas-processing plant. This article begins a four-part series describing the most common H/sub 2/S scavengers available to the natural gas-producing industry. Advantages, disadvantages, health and safety aspects, case histories, design guidelines, and economics of these scavengers will be addressed. Currently available, nonregenerative scavengers for small-plant H/sub 2/S removal may be categorized into four groups: Formaldehyde-methanol-based, metallic oxide-based, caustic-based, and other processes.

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

    NASA Astrophysics Data System (ADS)

    Herrington, Jason S.; Hays, Michael D.

    2012-08-01

    There is high demand for accurate and reliable airborne carbonyl measurement methods due to the human and environmental health impacts of carbonyls and their effects on atmospheric chemistry. Standardized 2,4-dinitrophenylhydrazine (DNPH)-based sampling methods are frequently applied for measuring gaseous carbonyls in the atmospheric environment. However, there are multiple short-comings associated with these methods that detract from an accurate understanding of carbonyl-related exposure, health effects, and atmospheric chemistry. The purpose of this brief technical communication is to highlight these method challenges and their influence on national ambient monitoring networks, and to provide a logical path forward for accurate carbonyl measurement. This manuscript focuses on three specific carbonyl compounds of high toxicological interest—formaldehyde, acetaldehyde, and acrolein. Further method testing and development, the revision of standardized methods, and the plausibility of introducing novel technology for these carbonyls are considered elements of the path forward. The consolidation of this information is important because it seems clear that carbonyl data produced utilizing DNPH-based methods are being reported without acknowledgment of the method short-comings or how to best address them.

  6. Cytotoxic effects of methanol, formaldehyde, and formate on dissociated rat thymocytes: a possibility of aspartame toxicity.

    PubMed

    Oyama, Y; Sakai, H; Arata, T; Okano, Y; Akaike, N; Sakai, K; Noda, K

    2002-01-01

    Aspartame is a widely used artificial sweetener added to many soft beverages and its usage is increasing in health-conscious societies. Upon ingestion, this artificial sweetener produces methanol as a metabolite. In order to examine the possibility of aspartame toxicity, the effects of methanol and its metabolites (formaldehyde and formate) on dissociated rat thymocytes were studied by flow cytometry. While methanol and formate did not affect cell viability in the physiological pH range, formaldehyde at 1-3 mmol/L started to induce cell death. Further increase in formaldehyde concentration produced a dose-dependent decrease in cell viability. Formaldehyde at 1 mmol/L or more greatly reduced cellular content of glutathione, possibly increasing cell vulnerability to oxidative stress. Furthermore, formaldehyde at 3 mmol/L or more significantly increased intracellular concentration of Ca2+ ([Ca2+]i) in a dose-dependent manner. Threshold concentrations of formaldehyde, a metabolite of methanol, that affected the [Ca2+]i and cellular glutathione content were slightly higher than the blood concentrations of methanol previously reported in subjects administered abuse doses of aspartame. It is suggested that aspartame at abuse doses is harmless to humans.

  7. 40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... flow through the particulate filters, methanol impingers and formaldehyde impingers. These instruments... calibration; particulate, methanol, and formaldehyde measurement. 86.1320-90 Section 86.1320-90 Protection of... AND IN-USE HIGHWAY VEHICLES AND ENGINES (CONTINUED) Emission Regulations for New Otto-Cycle and...

  8. 40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... flow through the particulate filters, methanol impingers and formaldehyde impingers. These instruments... calibration; particulate, methanol, and formaldehyde measurement. 86.1320-90 Section 86.1320-90 Protection of... AND IN-USE HIGHWAY VEHICLES AND ENGINES (CONTINUED) Emission Regulations for New Otto-Cycle and...

  9. 40 CFR 86.1320-90 - Gas meter or flow instrumentation calibration; particulate, methanol, and formaldehyde measurement.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... flow through the particulate filters, methanol impingers and formaldehyde impingers. These instruments... calibration; particulate, methanol, and formaldehyde measurement. 86.1320-90 Section 86.1320-90 Protection of... AND IN-USE HIGHWAY VEHICLES AND ENGINES (CONTINUED) Emission Regulations for New Otto-Cycle and...

  10. Water co-catalyzed selective dehydrogenation of methanol to formaldehyde and hydrogen

    NASA Astrophysics Data System (ADS)

    Shan, Junjun; Lucci, Felicia R.; Liu, Jilei; El-Soda, Mostafa; Marcinkowski, Matthew D.; Allard, Lawrence F.; Sykes, E. Charles H.; Flytzani-Stephanopoulos, Maria

    2016-08-01

    The non-oxidative dehydrogenation of methanol to formaldehyde is considered a promising method to produce formaldehyde and clean hydrogen gas. Although Cu-based catalysts have an excellent catalytic activity in the oxidative dehydrogenation of methanol, metallic Cu is commonly believed to be unreactive for the dehydrogenation of methanol in the absence of oxygen adatoms or oxidized copper. Herein we show that metallic Cu can catalyze the dehydrogenation of methanol in the absence of oxygen adatoms by using water as a co-catalyst both under realistic reaction conditions using silica-supported PtCu nanoparticles in a flow reactor system at temperatures below 250 °C, and in ultra-high vacuum using model PtCu(111) catalysts. Adding small amounts of isolated Pt atoms into the Cu surface to form PtCu single atom alloys (SAAs) greatly enhances the dehydrogenation activity of Cu. Under the same reaction conditions, the yields of formaldehyde from PtCu SAA nanoparticles are more than one order of magnitude higher than on the Cu nanoparticles, indicating a significant promotional effect of individual, isolated Pt atoms. Moreover, this study also shows the unexpected role of water in the activation of methanol. Water, a catalyst for methanol dehydrogenation at low temperatures, becomes a reactant in the methanol steam reforming reactions only at higher temperatures over the same metal catalyst.

  11. Silver catalysts in the partial oxidation of methanol to formaldehyde

    SciTech Connect

    Devochkin, A.N.; Pestryakov, A.N.; Kurina, L.N.; Sakharov, A.A.

    1992-07-20

    A comparative study of the catalytic activity of supported (Ag/pumice, LNKh-M) and bulk (Ag{sub cryst}, SD, KS) catalysts for methanol oxidation was carried out. The effect of technological parameters on the partial oxidation of methanol was studied. The optimum conditions for conducting the process on the catalysts studied were determined. 5 refs., 1 tab.

  12. [Features of dyslipidemia development and insulin resistance in female workers engaged in methanol and formaldehyde production].

    PubMed

    Taranenko, L A

    2013-01-01

    The article covers data on analyzing occupational risk of carbohydrate and lipid metabolism in female workers exosed to methanol and formaldehyde. Findings are that increased contents of the studied chemicals in the air of workplace cause more probable dyslipidemia, insuline resistence in peri-menopausal female workers, these disorders have reliable correlation with occupation. PMID:24640083

  13. Evidence for Conversion of Methanol to Formaldehyde in Nonhuman Primate Brain

    PubMed Central

    Zhai, Rongwei; Zheng, Na; Rizak, Joshua; Hu, Xintian

    2016-01-01

    Many studies have reported that methanol toxicity to primates is mainly associated with its metabolites, formaldehyde (FA) and formic acid. While methanol metabolism and toxicology have been best studied in peripheral organs, little study has focused on the brain and no study has reported experimental evidence that demonstrates transformation of methanol into FA in the primate brain. In this study, three rhesus macaques were given a single intracerebroventricular injection of methanol to investigate whether a metabolic process of methanol to FA occurs in nonhuman primate brain. Levels of FA in cerebrospinal fluid (CSF) were then assessed at different time points. A significant increase of FA levels was found at the 18th hour following a methanol injection. Moreover, the FA level returned to a normal physiological level at the 30th hour after the injection. These findings provide direct evidence that methanol is oxidized to FA in nonhuman primate brain and that a portion of the FA generated is released out of the brain cells. This study suggests that FA is produced from methanol metabolic processes in the nonhuman primate brain and that FA may play a significant role in methanol neurotoxicology. PMID:27066393

  14. Formaldehyde

    NASA Astrophysics Data System (ADS)

    Kowatsch, Stefan

    Formaldehyde, as an aqueous solution ranging from 37 to 50 wt%, continues to be the preferred aldehyde for reaction with phenol for the preparation of phenolic resins. Over 30 million metric tons of formaldehyde represent the global worldwide consumption of formaldehyde for an array of products, besides phenolic resins. These include urea formaldehyde resins, melamine formaldehyde resins, polyacetal resins, methylenebis (4-phenyl isocyanate), butanediol, pentaerythritol, and others.

  15. Biotransformation of methanol and formaldehyde by bacteria isolated from clouds. Comparison with radical chemistry

    NASA Astrophysics Data System (ADS)

    Husárová, Slavomíra; Vaïtilingom, Mickaël; Deguillaume, Laurent; Traikia, Mounir; Vinatier, Virginie; Sancelme, Martine; Amato, Pierre; Matulová, Mária; Delort, Anne-Marie

    2011-10-01

    The kinetics of biodegradation of methanol and formaldehyde in phosphate buffer at pH 7 by 4 bacterial strains ( Pseudomonas spp., Bacillus sp. and Frigoribacterium sp.) isolated from cloud water at the puy de Dôme mountain have been investigated using 1H and 13C NMR spectroscopy. We showed that biodegradation occurred at 5 °C and 17 °C, respectively average and summertime temperature considered within the cloud system at this site. They ranged from 10 -19 to 10 -21 mol cell -1 s -1 both at 5 and 17 °C for formaldehyde, and from 10 -21 to 10 -23 mol cell -1 s -1 at 5 and 17 °C for methanol. Metabolic intermediates were identified, with notably production of C3 compounds (glycerol, 1,2- and 1,3-propanediol) from formaldehyde by the strain Bacillus sp. In order to evaluate to which extent microbiological oxidation of organic compounds has to be considered as an alternative route to radical chemistry in cloud water, the biodegradation rates measured were compared with rates related to the reactivity of organic species with free radicals rad OH (daytime chemistry) and NO 3rad (nighttime chemistry) under two cloud situations (urban and remote cases). Clearly, measured biological and chemical reaction rates were in the same range of magnitude and their relative contribution varies according to the scenarios we tested, including the temperature of the clouds (5 or 17 °C), the category of the clouds (urban and remote) and the diurnal cycle (day and nighttime). Except for the degradation of methanol at 5 °C in remote clouds, our results show that biotransformation processes could be the main sink for C1 compounds in liquid clouds ( T ≥ 5 °C ≡ "warm cloud") during the night and both in polluted and non polluted clouds.

  16. A small-scale, inexpensive method for detecting formaldehyde or methanol in biochemical reactions containing interfering substances.

    PubMed

    Jiang, Wen Zhi; Adamec, Jiri; Weeks, Donald P

    2013-11-15

    A simple, inexpensive microdistillation device is described for capturing methanol or formaldehyde as end products of biochemical reactions or in environmental samples. We demonstrate that the microdistillation protocol, coupled with the use of alcohol oxidase and the formaldehyde-sensitive reagent Purpald (4-amino-3-hydrazino-5-mercapto-1,2,4-triazole), serves as a quick and inexpensive alternative to chromatographic and mass spectrometer analyses for determining if formaldehyde or methanol is a product of reactions that contain substances that interfere with the Purpald reaction. These techniques were used to affirm formaldehyde as the end product of the dicamba monooxygenase-catalyzed O-demethylation of the herbicide dicamba (2-methoxy-3,6-dichlorobenzoic acid). PMID:23938775

  17. A small-scale, inexpensive method for detecting formaldehyde or methanol in biochemical reactions containing interfering substances.

    PubMed

    Jiang, Wen Zhi; Adamec, Jiri; Weeks, Donald P

    2013-11-15

    A simple, inexpensive microdistillation device is described for capturing methanol or formaldehyde as end products of biochemical reactions or in environmental samples. We demonstrate that the microdistillation protocol, coupled with the use of alcohol oxidase and the formaldehyde-sensitive reagent Purpald (4-amino-3-hydrazino-5-mercapto-1,2,4-triazole), serves as a quick and inexpensive alternative to chromatographic and mass spectrometer analyses for determining if formaldehyde or methanol is a product of reactions that contain substances that interfere with the Purpald reaction. These techniques were used to affirm formaldehyde as the end product of the dicamba monooxygenase-catalyzed O-demethylation of the herbicide dicamba (2-methoxy-3,6-dichlorobenzoic acid).

  18. Fate of partially oxidised hydrocarbons in the UT: Reaction of OH with acetaldehyde, formaldehyde and methanol.

    NASA Astrophysics Data System (ADS)

    Sivakumaran, V.; Cameron, M.; Dillon, T. J.; Hoelscher, D.; Horowitz, A.; Crowley, J. N.

    2003-04-01

    Partially Oxidised Hydrocarbons (POH) strongly influence the formation of HOx and ozone in the upper troposphere [1]. POH are formed in the atmosphere as intermediates in the oxidation of methane non-methane hydrocarbons and are also directly emitted in the boundary layer as a result of biogenic processes and from combustion systems. Although the OH initiated oxidation is an important sink of many POH, the available kinetic data for the reaction of OH with formaldehyde, acetaldehyde and methanol relevant to upper tropospheric temperatures (210-240 K) is limited, and the measured rate constants have a large uncertainties [2]. Also there is a lack of definitive product and mechanistic data for these reactions. We present new, highly accurate rate constants for reaction of OH with formaldehyde, acetaldehyde and methanol at temperatures down to 201 K. We also present direct measurements of branching ratios to the various thermodynamically accessible product channels of these reactions. 1. Singh, H., et al., Evidence from the Pacific troposphere for large global sources of oxygenated organic compounds. Nature, 410, 2001, 1078-1081. 2. Atkinson, R., et al., Evaluated kinetic and photochemical data for atmospheric chemistry, organic species: Supplement VII. IUPAC subcommittee on gas kinetic data evaluation for atmospheric chemistry. J. Phys. Chem. Ref. Data, 28, 1999. 191-393.

  19. Direct use of methanol as an alternative to formaldehyde for the synthesis of 3,3'-bisindolylmethanes (3,3'-BIMs).

    PubMed

    Sun, Chunlou; Zou, Xiaoyuan; Li, Feng

    2013-10-11

    Red card for formaldehyde: The direct coupling of indoles with methanol to 3,3'-bisindolylmethanes with good to excellent yields was accomplished by using a commercially available iridium complex. This study demonstrates the potential of direct use of methanol as an alternative to formaldehyde for synthetic transformations. PMID:24108592

  20. The Active Molybdenum Oxide Phase in the Methanol Oxidation to Formaldehyde (Formox Process): A DFT Study.

    PubMed

    Rellán-Piñeiro, Marcos; López, Núria

    2015-07-01

    Methanol is oxidised to formaldehyde by the Formox process, in which molybdenum oxides, usually doped with iron, are the catalyst. The active phase of the catalysts and the reasons for the selectivity observed are still unknown. We present a density functional theory based study that indicates the unique character of Mo(VI)¢Mo(IV) pairs as the most active and selective sites and indicates the active sites on the surface, the controlling factors of selectivity, and the role of the dopant. Iron reduces the energy requirements of the redox Mo(VI)¢Mo(IV) pair by acting as an electron reservoir that sets in if required. Our present study paves the way towards a better understanding of the process.

  1. Formaldehyde

    Integrated Risk Information System (IRIS)

    Formaldehyde ; CASRN 50 - 00 - 0 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 Effec

  2. Growth of Bacillus methanolicus in 2 M methanol at 50 °C: the effect of high methanol concentration on gene regulation of enzymes involved in formaldehyde detoxification by the ribulose monophosphate pathway.

    PubMed

    Bozdag, Ahmet; Komives, Claire; Flickinger, Michael C

    2015-07-01

    Bacillus methanolicus MGA3 is a Gram-positive aerobic methylotroph growing optimally at 50-53°C. Methylotrophy in B. methanolicus is encoded on pBM19 and by two chromosomal copies of the methanol dehydrogenase (mdh), hexulose phosphate synthase (hps) and phosphohexuloisomerase (phi) genes. However, there are no published studies on the regulation of methylotrophy or the dominant mechanism of detoxification of intracellular formaldehyde in response to high methanol concentration. The µ max of B. methanolicus MGA3 was assessed on methanol, mannitol and glucose. B. methanolicus achieved a µ max at 25 mM initial methanol of 0.65 ± 0.007 h(-1), which decreased to 0.231 ± 0.004 h(-1) at 2 M initial methanol. Slow growth was also observed with initial methanol concentrations of >2 M. The µ max on mannitol and glucose are 0.532 ± 0.002 and 0.336 ± 0.003 h(-1), respectively. Spiking cultures with additional methanol (100 mM) did not disturb the growth rate of methanol-grown cells, whereas, a 50 mM methanol spike halted the growth in mannitol. Surprisingly, growth in methanol was inhibited by 1 mM formaldehyde, while mannitol-grown cells tolerated 2 mM. Moreover, mannitol-grown cells removed formaldehyde faster than methanol-grown cells. Further, we show that methanol oxidation in B. methanolicus MGA3 is mainly carried out by the pBM19-encoded mdh. Formaldehyde and formate addition down-regulate the mdh and hps genes in methanol-grown cells. Similarly, they down-regulate mdh genes in mannitol-grown cells, but up-regulate hps. Phosphofructokinase (pfk) is up-regulated in both methanol and mannitol-grown cells, which suggests that pfk may be a possible synthetic methylotrophy target to reduce formaldehyde growth toxicity at high methanol concentrations.

  3. A density functional theory study of the oxidation of methanol to formaldehyde over vanadia supported on silica, titania, and zirconia

    SciTech Connect

    Khaliullin, Rustam Z.; Bell, Alexis T.

    2002-09-05

    Density functional theory was used to investigate the mechanism and kinetics of methanol oxidation to formaldehyde over vanadia supported on silica, titania, and zirconia. The catalytically active site was modeled as an isolated VO{sub 4} unit attached to the support. The calculated geometry and vibrational frequencies of the active site are in good agreement with experimental measurements both for model compounds and oxide-supported vanadia. Methanol adsorption is found to occur preferentially with the rupture of a V-O-M bond (M = Si, Ti, Zr) and with preferential attachment of a methoxy group to V. The vibrational frequencies of the methoxy group are in good agreement with those observed experimentally as are the calculated isobars. The formation of formaldehyde is assumed to occur via the transfer of an H atom of a methoxy group to the O atom of the V=O group. The activation energy for this process is found to be in the range of 199-214 kJ/mol and apparent activation energies for the overall oxidation of methanol to formaldehyde are predicted to lie in the range of 112-123 kJ/mol, which is significantly higher than that found experimentally. Moreover, the predicted turnover frequency (TOF) for methanol oxidation is found to be essentially independent of support composition, whereas experiments show that the TOF is 10{sup 3} greater for titania- and zirconia-supported vanadia than for silica-supported vanadia. Based on these findings, it is proposed that the formation of formaldehyde from methoxy groups may require pairs of adjacent VO{sub 4} groups or V{sub 2}O{sub 7} dimer structures.

  4. New reactions of paraformaldehyde and formaldehyde with inorganic compounds

    NASA Technical Reports Server (NTRS)

    Becker, R. S.; Bercovici, T.; Hong, K.

    1974-01-01

    Both paraformaldehyde and formaldehyde undergo reactions in the presence of several inorganic compounds to generate a variety of interesting organic products that can be important in chemical evolutionary processes. Some examples are acrolein, acetaldehyde, methyl formate, methanol, glycolaldehyde and formic acid. The organic compounds are produced at temperatures as low as 56 C and in high yield (up to 75%). The quantity produced depends principally on the nature of the inorganic compound, the ratio of the inorganic compound to paraformaldehyde, temperature and reaction time. The percent distribution of product depends on some of the foregoing factors.

  5. Biostimulation by methanol enables the methylotrophic yeasts Hansenula polymorpha and Trichosporon sp. to reveal high formaldehyde biodegradation potential as well as to adapt to this toxic pollutant.

    PubMed

    Kaszycki, Paweł; Walski, Tomasz; Hachicho, Nancy; Heipieper, Hermann J

    2013-06-01

    The methylotrophic yeasts Hansenula polymorpha and Trichosporon sp. revealed enhanced biodegradation capability of exogenously applied formaldehyde (Fd) upon biostimulation achieved by the presence of methanol, as compared to glucose. Upon growth on either of the above substrates, the strains proved to produce the activity of glutathione-dependent formaldehyde dehydrogenase-the enzyme known to control the biooxidative step of Fd detoxification. However, in the absence of methanol, the yeasts' tolerance to Fd was decreased, and the elevated sensitivity was especially pronounced for Trichosporon sp. Both strains responded to the methanol and/or Fd treatment by increasing their unsaturation index (UI) at xenobiotic levels below minimal inhibitory concentrations. This indicated that the UI changes effected from the de novo synthesis of (poly) unsaturated fatty acids carried out by viable cells. It is concluded that the yeast cell response to Fd intoxication involves stress reaction at the level of membranes. Fluidization of the lipid bilayer as promoted by methanol is suggested as a significant adaptive mechanism increasing the overall fitness enabling to cope with the formaldehyde xenobiotic via biodegradative pathway of C1-compound metabolism.

  6. Acrolein health effects.

    PubMed

    Faroon, O; Roney, N; Taylor, J; Ashizawa, A; Lumpkin, M H; Plewak, D J

    2008-08-01

    Acrolein is a chemical used as an intermediate reactive aldehyde in chemical industry. It is used for synthesis of many organic substances, methionine production, and methyl chloride refrigerant. The general population is exposed to acrolein via smoking, second-hand smoke, exposure to wood and plastic smoke. Firefighters and population living or working in areas with heavy automotive traffic may expose to higher level of acrolein via inhalation of smoke or automotive exhaust. Degradation of acrolein in all environmental media occurs rapidly, therefore, environmental accumulation is not expected. Acrolein degrade in 6A days when applied to surface water, and it has not been found as a contaminant in municipal drinking water. Acrolein vapor may cause eye, nasal and respiratory tract irritations in low level exposure. A decrease in breathing rate was reported by volunteers acutely exposed to 0.3A ppm of acrolein. At similar level, mild nasal epithelial dysplasia, necrosis, and focal basal cell metaplasia have been observed in rats. The acrolein effects on gastrointestinal mucosa in the animals include epithelial hyperplasia, ulceration, and hemorrhage. The severity of the effects is dose dependent. Acrolein induces the respiratory, ocular, and gastrointestinal irritations by inducing the release of peptides in nerve terminals innervating these systems. Levels of acrolein between 22 and 249 ppm for 10 min induced a dose-related decrease in substance P (a short-chain polypeptide that functions as a neurotransmitter or neuromodulator).

  7. Dehydrogenation of methanol to formaldehyde catalyzed by pristine and defective ceria surfaces

    DOE PAGES

    Beste, Ariana; Overbury, Steven H.

    2016-03-09

    We have explored the dehydrogenation of methoxy on pristine and defective (111), (100), and (110) ceria surfaces with density functional methods. Methanol conversion is used as a probe reaction to understand structure sensitivity of the oxide catalysis. Differences in reaction selectivity have been observed experimentally as a function of crystallographically exposed faces and degree of reduction. We find that the barrier for carbon-hydrogen cleavage in methoxy is similar for the pristine and defective (111), (100), and (110) surfaces. However, there are large differences in the stability of the surface intermediates on the different surfaces. The variations in experimentally observed productmore » selectivities are a consequence of the interplay between barrier controlled bond cleavage and desorption processes. Ultimately, subtle differences in activation energies for carbon-hydrogen cleavage on the different crystallographic faces of ceria could not be correlated with structural or electronic descriptors.« less

  8. Formaldehyde and methanol formation from reaction of carbon monoxide and hydrogen on neutral Fe2S2 clusters in the gas phase.

    PubMed

    Yin, Shi; Wang, Zhechen; Bernstein, Elliot R

    2013-04-01

    Reaction of CO with H2 on neutral FemSn clusters in a fast flow reactor is investigated both experimentally and theoretically. Single photon ionization at 118 nm is used to detect neutral cluster distributions through time of flight mass spectrometry. FemSn clusters are generated through laser ablation of a mixed iron-sulfur target in the presence of a pure helium carrier gas. A strong size dependent reactivity of (FeS)m clusters toward CO is characterized. The reaction FeS + CO → Fe + OCS is found for the FeS cluster, and the association product Fe2S2CO is observed for the Fe2S2 cluster. Products Fe2S2(13)COH2 and Fe2S2(13)COH4 are identified for reactions of (13)CO and H2 on Fe2S2 clusters: this suggests that the Fe2S2 cluster has a high catalytic activity for hydrogenation reactions of CO to form formaldehyde and methanol. Density functional theory (DFT) calculations are performed to explore the potential energy surfaces for the two reactions: Fe2S2 + CO + 2H2 → Fe2S2 + CH3OH; and Fe2S2 + CO + H2 → Fe2S2 + CH2O. A barrierless, thermodynamically favorable pathway is obtained for both catalytic processes. Catalytic cycles for formaldehyde and methanol formation from CO and H2 on a Fe2S2 cluster are proposed based on our experimental and theoretical investigations. The various reaction mechanisms explored by DFT are in good agreement with the experimental results. Condensed phase iron sulfide, which contains exposed Fe2S2 units on its surface, is suggested to be a good catalyst for low temperature formaldehyde/methanol synthesis.

  9. Atmospheric chemistry of toxic contaminants. 3. Unsaturated aliphatics: Acrolein, acrylonitrile, maleic anhydride

    SciTech Connect

    Grosjean, D. )

    1990-12-01

    Detailed mechanisms are outlined for the chemical reactions that contribute to in-situ formation and atmospheric removal of the unsaturated aliphatic contaminants acrolein, acrylonitrile, and maleic anhydride. In-situ formation of small amounts of acrolein and maleic anhydride may involve the reaction of OH (and O{sub 3}) with 1,3-dienes and the reaction of OH with aromatic hydrocarbons, respectively. There is no known pathway for in-situ formation of acrylonitrile. Rapid removal of acrolein (half-life = less than one day) and of maleic anhydride (half-life = several hours) is expected from their rapid reactions with OH (major), O{sub 3}, and NO{sub 3}. These reactions lead to formaldehyde and glyoxal from acrolein and to dicarbonyls from maleic anhydride. Acrylonitrile is removed at a slower rate (half-life = 2-7 days) by reaction with OH, leading to formaldehyde and formyl cyanide.

  10. Methanol

    Integrated Risk Information System (IRIS)

    Methanol ; CASRN 67 - 56 - 1 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 Effects )

  11. Emissions of formaldehyde, acetic acid, methanol, and other trace gases from biomass fires in North Carolina measured by airborne Fourier transform infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Yokelson, R. J.; Goode, J. G.; Ward, D. E.; Susott, R. A.; Babbitt, R. E.; Wade, D. D.; Bertschi, I.; Griffith, D. W. T.; Hao, W. M.

    1999-12-01

    Biomass burning is an important source of many trace gases in the global troposphere. We have constructed an airborne trace gas measurement system consisting of a Fourier transform infrared spectrometer (FTIR) coupled to a "flow-through" multipass cell (AFTIR) and installed it on a U.S. Department of Agriculture Forest Service King Air B-90. The first measurements with the new system were conducted in North Carolina during April 1997 on large, isolated biomass fire plumes. Simultaneous measurements included Global Positioning System (GPS); airborne sonde; particle light scattering, CO, and CO2; and integrated filter and canister samples. AFTIR spectra acquired within a few kilometers of the fires yielded excess mixing ratios for 10 of the most common trace gases in the smoke: water, carbon dioxide, carbon monoxide, methane, formaldehyde, acetic acid, formic acid, methanol, ethylene, and ammonia. Emission ratios to carbon monoxide for formaldehyde, acetic acid, and methanol were each 2.5±1%. This is in excellent agreement with (and confirms the relevance of) our results from laboratory fires. However, these ratios are significantly higher than the emission ratios reported for these compounds in some previous studies of "fresh" smoke. We present a simple photochemical model calculation that suggests that oxygenated organic compounds should be included in the assessment of ozone formation in smoke plumes. Our measured emission factors indicate that biomass fires could account for a significant portion of the oxygenated organic compounds and HOx present in the tropical troposphere during the dry season. Our fire measurements, along with recent measurements of oxygenated biogenic emissions and oxygenated organic compounds in the free troposphere, indicate that these rarely measured compounds play a major, but poorly understood, role in the HOx, NOx, and O3 chemistry of the troposphere.

  12. Formaldehyde Stress Responses in Bacterial Pathogens

    PubMed Central

    Chen, Nathan H.; Djoko, Karrera Y.; Veyrier, Frédéric J.; McEwan, Alastair G.

    2016-01-01

    Formaldehyde is the simplest of all aldehydes and is highly cytotoxic. Its use and associated dangers from environmental exposure have been well documented. Detoxification systems for formaldehyde are found throughout the biological world and they are especially important in methylotrophic bacteria, which generate this compound as part of their metabolism of methanol. Formaldehyde metabolizing systems can be divided into those dependent upon pterin cofactors, sugar phosphates and those dependent upon glutathione. The more prevalent thiol-dependent formaldehyde detoxification system is found in many bacterial pathogens, almost all of which do not metabolize methane or methanol. This review describes the endogenous and exogenous sources of formaldehyde, its toxic effects and mechanisms of detoxification. The methods of formaldehyde sensing are also described with a focus on the formaldehyde responsive transcription factors HxlR, FrmR, and NmlR. Finally, the physiological relevance of detoxification systems for formaldehyde in bacterial pathogens is discussed. PMID:26973631

  13. [Methanol metabolism in plants].

    PubMed

    Stepanov, S S; Zolotar'ova, O K

    2011-01-01

    Methabolism of methanol in plant organisms is considered in the paper. Enzymes of consecutive oxidation of methanol and enzymes responsible for incorporation of carbon from methanol molecule to methyl groups of phospholipids, carboxylic acids and carbohydrates have been described. The peculiarity of plant organisms is in interaction of reactions of methanol transformation with pathways of photorespiration and C1-metabolism and in the capacity to use methanol carbon to form organic matter through photosynthesis. The inclusion of methanol metabolites in anabolic processes occurs at the level of formaldehyde and formiate. As a result, exogenous methanol at low concentrations can stimulate the photosynthetic efficiency of plants.

  14. Having a multi facetted approach to complex organic molecules formation: the European COST initiative ‘Our Astochemical History’ and the formaldehyde/methanol formation example

    NASA Astrophysics Data System (ADS)

    Wiesenfeld, Laurent; Ceccarelli, Cecilia; Lefloch, Bertrand

    2015-08-01

    Formaldehyde (H2CO) and methanol (CH3OH) are among the few molecules that have been detected in the solid phase, in the icy mantles that cover interstellar grains. They have been also widely observed in the gas phase of many cold gases, with high somewhat comparable abundances. The synthetic routes leading from ubiquitous CO to these hydrogenated CO molecules have been widely discussed in the literature. Also, deuterated (and per-deuterated) isotopomers of both H2CO and CH3OH have been detected, with very high enrichment in D over the 10-5 cosmic abundance of D with respect to H.In this presentation, we wish to review the first steps of the hysdrogenation processes and describe how they have been recently treated, in the laboratory, the modelling and in theoretical chemical physics.We take and discuss this example as the perfect illustration of the necessity of having a multifaceted approach to the problems we face:1. How to hydrogenated CO towards H2CO: gas phase/solid phase chemistry. (Peters29013; Rimola2014)2. How to detect H2CO / HDCO in the gas phase, in a quantitative manner: LTE vs. non-LTE excitation. (Wiesenfeld2014)3. What is the role of laboratory experiments, how relevant are they, and more important, how challenging are they? (Hama2013)4. Is deuterium enrichment a good tracer for the history ? (Taquet2013)Some of the questions have received an answer in recent years, and we shall briefly describe those, with special emphasis to a joint chemistry-astrophysics approach.We describe the European COST network ‘Our Astrochemical History’ (http://prague2015astrohistory.vscht.cz/) , whichbrings together specialists of many areas of chemistry together with astronomy, in order to address this kind of problem. Succeeding former European initiatives that shaped the field of Astrochemistry, it focussses on the molecular evolution towards higher complexity and aim sat delivering new schemes for physical chemistry at large, like chemistry of transient species

  15. Controlling formaldehyde emissions with boiler ash.

    PubMed

    Cowan, Jennifer; Abu-Daabes, Malyuba; Banerjee, Sujit

    2005-07-01

    Fluidized wood ash reduces formaldehyde in air from about 20 to <1 ppmv. Methanol is removed to a much lower extent. The efficiency of formaldehyde reduction increases with increasing moisture content of the ash. Sorption of formaldehyde to ash can be substantially accounted for by partitioning to the water contained in the ash followed by rate-controlling binding to the ash solids. Adsorption occurs at temperatures of up to 165 degrees C; oxidation predominates thereafter. It is proposed that formaldehyde could be stripped from an air stream in a fluidized bed containing ash, which could then be returned to a boiler to incinerate the formaldehyde.

  16. Acrolein induces oxidative stress in brain mitochondria.

    PubMed

    Luo, Jian; Shi, Riyi

    2005-02-01

    Acrolein, a byproduct of lipid peroxidation, has been shown to inflict significant structural and functional damage to isolated guinea pig spinal cord. Reactive oxygen species (ROS) are thought to mediate such detrimental effects. The current study demonstrates that acrolein can directly stimulate mitochondrial oxidative stress. Specifically, exposure of purified brain mitochondria to acrolein resulted in a dose-dependent increase of ROS and decreases in glutathione content and aconitase activity. This effect was not accompanied by significant intramitochondrial calcium influx or mitochondrial permeability transition, but rather by impaired function of the mitochondrial electron transport system. As well, we detected a significant inhibition of mitochondrial adenine nucleotide translocase (ANT) in the presence of acrolein. This inhibition of ANT likely contributes to acrolein-induced ROS elevation since application of atractyloside, a specific ANT inhibitor, induced significant increase of ROS. We hypothesize that inhibition of ANT may mediate, in part, the acrolein-induced ROS increase in mitochondria.

  17. Acrolein health effects. Final report

    SciTech Connect

    Carson, B.L.; Beall, C.M.; Ellis, H.V. III; Baker, L.H.; Herndon, B.L.

    1981-09-01

    Health effects literature primarily related to inhalation exposures to acrolein was collected, evaluated, tabulated, and summarized. Approximately 125 documents were collected from computerized and manual literature searches covering the period 1911-1981. Pharmacologists and an M.D. epidemiologist rated the documents according to their applicabality to the study and their methodology. The approximately 45 documents considered useful for deriving a range of concern for human exposure to acrolein from automotive emissions were tabulated. The pages of tables detail the results of acute, repeated dose, and chronic testing of mice, hamsters, rats, guinea pigs, chickens, rabbits, cats, monkeys, dogs, and humans as well as human occupational and accidental studies. Most of the documents evaluated are described in an annotated bibliography.

  18. Formaldehyde-induced shrinkage of rat thymocytes.

    PubMed

    Nakao, Hiromi; Umebayashi, Chisato; Nakata, Mami; Nishizaki, Yasutaka; Noda, Katuhiko; Okano, Yoshiro; Oyama, Yasuo

    2003-01-01

    To test the possibility that micromolar formaldehyde, a metabolite of methanol derived from aspartame, exerts cytotoxicity, its effect on rat thymocytes was examined under the in vitro condition using a flow cytometer. Incubation of thymocytes with formaldehyde at 100 micro M or more for 24 h significantly increased the populations of shrunken cells and cells with hypodiploid DNA. The peak blood concentration of methanol in human subjects administered abuse doses of aspartame has been reported to exceed 2 mg/dL (625 micro M). It would increase the population of thymocytes undergoing apoptosis if formaldehyde at 100 micro M or more appears in the blood after administration of aspartame.

  19. IRIS TOXICOLOGICAL REVIEW OF ACROLEIN (2003 Final)

    EPA Science Inventory

    EPA is announcing 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 Quickview have also been added to the IRIS Database.

  20. Primary photochemical processes of acrolein. Final report

    SciTech Connect

    Gardner, E.P.; Sperry, P.D.; Calvert, J.G.

    1986-01-01

    Pollutants are removed from the atmosphere in a number of ways: they can react with OH and O/sub 3/, they can be dry and wet deposited, photodissociate through solar radiation, or they can be biodegraded. The report presents the photodissociation processes of acrolein. Quantum yields of acrolein loss are given. The dominant reactions in the lower troposphere are the formation of C/sub 2/H/sub 4/ and CO. Also produced are CH/sub 2/-CHCHO, H, CH/sub 2/CH, and HCO radicals but at lower quantum yields. Since the OH attack on acrolein is quite large (1.9 x 10/sup 11/ cu cm/molec s), ambient levels of OH (about 10/sup 6/ molecules/cu cm) will remove acrolein very rapidly (usually, about 15 hours). Thus, the major loss mechanism of acrolein in the troposphere is through OH attack, and the photodissociation process is of negligible importance.

  1. Fate and effects of acrolein.

    PubMed

    Ghilarducci, D P; Tjeerdema, R S

    1995-01-01

    Acrolein is a highly toxic, reactive, and irritating aldehyde that occurs as a product of organic pyrolysis, as a metabolite of a number of compounds, and as a residue in water when used for the control of aquatic organisms. It is an intermediate in the production of acrylic acid, DL-methionine, and numerous other agents. Its major direct use is as a biocide for the control of aquatic flora and fauna. It is introduced to the environment from a variety of sources, including organic combustion such as automobile exhaust, cigarette smoke, and manufacturing and cooking emissions, as well as direct biocidal applications. Organic combustion from both fixed and mobile sources is the significant source of acrolein in the atmosphere; it represents up to 8% of the total aldehydes generated from vehicles and residential fireplaces and 13% of total atmospheric aldehydes. This reactive aldehyde also occurs in organisms as a metabolite of allyl alcohol, allylamine, spermine, spermidine, and the anticancer drug cyclophosphamide, and as a product of UV radiation of the skin lipid triolein. Furthermore, small amounts are found in foods; when animal or vegetable fats are overheated, however, large amounts are produced. Most human contact occurs during exposure to smoke from cigarettes, automobiles, industrial processes, and structural and vegetation fires. Besides cigarette smoke, occupational exposures are a common mode of human contact, particularly in industries that involve combustion of organic compounds. Firefighters, in particular, are exposed to extremely high levels during the extinguishment and overhaul phases of their work. Water may contain significant levels of the herbicide. It has been found in paper mill and municipal effluents at 20-200 micrograms/L, and at 30 micrograms/L as far as 64 km downstream from the point of application. The USEPA-recommended water quality criteria for freshwater are only 1.2 micrograms/L (24-hr avg) and 2.7 micrograms/L (maximum ceiling

  2. Studies on methanol - oxidizing yeast. III. Enzyme.

    PubMed

    Volfová, O

    1975-01-01

    Oxidation of methanol, formaldehyde and formic acid was studied in cells and cell-free extract of the yeast Candida boidinii No. 11Bh. Methanol oxidase, an enzyme oxidizing methanol to formaldehyde, was formed inducibly after the addition of methanol to yeast cells. The oxidation of methanol by cell-free extract was dependent on the presence of oxygen and independent of any addition of nicotine-amide nucleotides. Temperature optimum for the oxidation of methanol to formaldehyde was 35 degrees C, pH optimum was 8.5. The Km for methanol was 0.8mM. The cell-free extract exhibited a broad substrate specificity towards primary alcohols (C1--C6). The activity of methanol oxidase was not inhibited by 1mM KCN, EDTA or monoiodoacetic acid. The strongest inhibitory action was exerted by p-chloromercuribenzoate. Both the cells and the cell-free extract contained catalase which participated in the oxidation of methanol to formaldehyde; the enzyme was constitutively formed by the yeast. The pH optimum for the degradation of H2O2 was in the same range as the optimum for methanol oxidation, viz. at 8.5. Catalase was more resistant to high pH than methanol oxidase. The cell-free extract contained also GSH-dependent NAD-formaldehyde dehydrogenase with Km = 0.29mM and NAD-formate dehydrogenase with Km = 55mM. PMID:240764

  3. Formaldehyde exposure affects growth and metabolism of common bean

    SciTech Connect

    Mutters, R.G.; Madore, M. ); Bytnerowicz, A. )

    1993-01-01

    Recent state and federal directives have slated a substantial increase in the use of methanol as an alternative to gasoline in both fleet and private vehicles in the coming decade. The incomplete combustion of methanol produces formaldehyde vapor, and catalytic converter technology that completely oxidizes formaldehyde has yet to be developed. The approach of this study was to use a range of methanol concentrations encompassing levels currently found or that may occur in the future in the ambient air of some heavily polluted areas to test the potential phytotoxicity of formaldehyde. The study had the following objectives: (1) design and build a formaldehyde vapor generator with sufficient capacity for long-term plant fumigations; (2) determine growth response of common bean to formaldehyde; (3) evaluate physiological and biochemical changes of bean plants associated with formaldehyde exposures. 20 refs., 2 figs., 2 tabs.

  4. 40 CFR 63.2262 - How do I conduct performance tests and establish operating requirements?

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... (TTE) conducted using Methods 204A through 204F of 40 CFR part 51, appendix M, which require three... acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde), THC, formaldehyde, or methanol in... (calculated as the sum of the emission rates of acetaldehyde, acrolein, formaldehyde, methanol, phenol,...

  5. Metabolic methanol: molecular pathways and physiological roles.

    PubMed

    Dorokhov, Yuri L; Shindyapina, Anastasia V; Sheshukova, Ekaterina V; Komarova, Tatiana V

    2015-04-01

    Methanol has been historically considered an exogenous product that leads only to pathological changes in the human body when consumed. However, in normal, healthy individuals, methanol and its short-lived oxidized product, formaldehyde, are naturally occurring compounds whose functions and origins have received limited attention. There are several sources of human physiological methanol. Fruits, vegetables, and alcoholic beverages are likely the main sources of exogenous methanol in the healthy human body. Metabolic methanol may occur as a result of fermentation by gut bacteria and metabolic processes involving S-adenosyl methionine. Regardless of its source, low levels of methanol in the body are maintained by physiological and metabolic clearance mechanisms. Although human blood contains small amounts of methanol and formaldehyde, the content of these molecules increases sharply after receiving even methanol-free ethanol, indicating an endogenous source of the metabolic methanol present at low levels in the blood regulated by a cluster of genes. Recent studies of the pathogenesis of neurological disorders indicate metabolic formaldehyde as a putative causative agent. The detection of increased formaldehyde content in the blood of both neurological patients and the elderly indicates the important role of genetic and biochemical mechanisms of maintaining low levels of methanol and formaldehyde.

  6. Pyrolysis of D-Glucose to Acrolein

    NASA Astrophysics Data System (ADS)

    Shen, Chong; Zhang, Igor Ying; Fu, Gang; Xu, Xin

    2011-06-01

    Despite of its great importance, the detailed molecular mechanism for carbohydrate pyrolysis remains poorly understood. We perform a density functional study with a newly developed XYG3 functional on the processes for D-glucose pyrolysis to acrolein. The most feasible reaction pathway starts from an isomerization from D-glucose to D-fructose, which then undergoes a cyclic Grob fragmentation, followed by a concerted electrocyclic dehydration to yield acrolein. This mechanism can account for the known experimental results.

  7. In vitro study on cytotoxicity and intracellular formaldehyde concentration changes after exposure to formaldehyde and its derivatives.

    PubMed

    Ke, Y J; Qin, X D; Zhang, Y C; Li, H; Li, R; Yuan, J L; Yang, X; Ding, S M

    2014-08-01

    HeLa cells were exposed to formaldehyde and its metabolic derivatives, methanol, formic acid, and acetaldehyde, to investigate that the toxicity of formaldehyde is not caused by the chemical group. After 1 h of treatment with formaldehyde, mitochondrial assays showed that low concentrations (e.g. 10 μmol/L) of formaldehyde promoted growth of the HeLa cells, while higher concentrations (e.g. ≥62.5 μmol/L) inhibited cell growth; while all four chemicals at a concentration of 125 μmol/L affected cell growth, formaldehyde affected the largest. Reactive oxygen species concentration increased with the concentration of the exposure chemical. The endogenous formaldehyde content increased the most in the formaldehyde group, but in other three groups, it did not increase as the exposure concentration increased. Expression of dehydrogenase (formaldehyde dehydrogenase (FDH)) in the formaldehyde (10.40) and methanol (10.60) groups increased significantly compared with the control (1), while it was similar to the control in formic acid (0.90) and acetaldehyde (1.10) groups. Our results suggest that formaldehyde could affect cell activity and even enter cells. Exposure to formaldehyde changes the endogenous formaldehyde concentration in cells within 24 h, and this induces expression of FDH for formaldehyde degradation to maintain the formaldehyde balance. The toxicity of formaldehyde is not caused by the carbon atoms in the aldehyde, hydroxyl, or carboxyl groups. Formaldehyde is hypothesized to be an important signaling molecule in the regulation of cell growth and maintenance of the endogenous formaldehyde level. PMID:24220877

  8. In vitro study on cytotoxicity and intracellular formaldehyde concentration changes after exposure to formaldehyde and its derivatives.

    PubMed

    Ke, Y J; Qin, X D; Zhang, Y C; Li, H; Li, R; Yuan, J L; Yang, X; Ding, S M

    2014-08-01

    HeLa cells were exposed to formaldehyde and its metabolic derivatives, methanol, formic acid, and acetaldehyde, to investigate that the toxicity of formaldehyde is not caused by the chemical group. After 1 h of treatment with formaldehyde, mitochondrial assays showed that low concentrations (e.g. 10 μmol/L) of formaldehyde promoted growth of the HeLa cells, while higher concentrations (e.g. ≥62.5 μmol/L) inhibited cell growth; while all four chemicals at a concentration of 125 μmol/L affected cell growth, formaldehyde affected the largest. Reactive oxygen species concentration increased with the concentration of the exposure chemical. The endogenous formaldehyde content increased the most in the formaldehyde group, but in other three groups, it did not increase as the exposure concentration increased. Expression of dehydrogenase (formaldehyde dehydrogenase (FDH)) in the formaldehyde (10.40) and methanol (10.60) groups increased significantly compared with the control (1), while it was similar to the control in formic acid (0.90) and acetaldehyde (1.10) groups. Our results suggest that formaldehyde could affect cell activity and even enter cells. Exposure to formaldehyde changes the endogenous formaldehyde concentration in cells within 24 h, and this induces expression of FDH for formaldehyde degradation to maintain the formaldehyde balance. The toxicity of formaldehyde is not caused by the carbon atoms in the aldehyde, hydroxyl, or carboxyl groups. Formaldehyde is hypothesized to be an important signaling molecule in the regulation of cell growth and maintenance of the endogenous formaldehyde level.

  9. The Reactions of Nitrogen Heterocycles with Acrolein: Scope and Prebiotic Significance

    NASA Astrophysics Data System (ADS)

    Cleaves, H. James

    2002-12-01

    It has been suggested that life began with a self-replicating RNA molecule. However, after much research into the prebiotic synthesis of RNA, the difficulties encountered have lead some to hypothesize that RNA was preceded by a simpler molecule, one more easily synthesized prebiotically. Many of the proposed alternative molecules are based on acrolein, since it reacts readily with nucleophiles, such as the nucleobases, via Michael addition and is readily synthesized from formaldehyde and acetaldehyde. Reports regarding the reactions of nucleobases with concentrated acrolein solutions suggest that this is a plausible reaction mechanism, though there are also reports that the "incorrect" isomers are obtained. The scope and kinetics of the reaction of acrolein with various nitrogen heterocycles are reported here. Reactions of pyrimidines often give N1 adducts as the major products. Reactions of purines often give N9 adducts in good yield. The reactions are rapid under neutral to slightly alkaline conditions, and proceed at low temperatures and dilutions. The implications of these findings for the origin of life are discussed.

  10. THE DISTRIBUTION OF DEUTERATED FORMALDEHYDE WITHIN ORION-KL

    SciTech Connect

    Favre, Cécile; Bergin, Edwin A.; Neill, Justin L.; Crockett, Nathan R.; Zhang, Qizhou; Lis, Dariusz C.

    2015-08-01

    We report the first high angular resolution imaging (3.″4 × 3.″0) of deuterated formaldehyde (HDCO) toward Orion-KL, carried out with the Submillimeter Array. We find that the spatial distribution of the formaldehyde emission systematically differs from that of methanol: while methanol is found toward the inner part of the region, HDCO is found in colder gas that wraps around the methanol emission on four sides. The HDCO/H{sub 2}CO ratios are determined to be 0.003–0.009 within the region, up to an order of magnitude higher than the D/H measured for methanol. These findings strengthen the previously suggested hypothesis that there are differences in the chemical pathways leading to HDCO (via deuterated gas-phase chemistry) and deuterated methanol (through conversion of formaldehyde into methanol on the surface of icy grain mantles)

  11. Concentrations of formaldehyde and other carbonyls in environments affected by incense burning.

    PubMed

    Ho, Steven Sai Hang; Yu, Jian Zhen

    2002-10-01

    Burning incense to pay homage to deities is common in Chinese homes and temples. Air samples were collected and analyzed for carbonyls from a home and a temple in Hong Kong where incense burning occurs on a daily basis. Carbonyls in the air were trapped on a solid sorbent coated with O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine, followed by thermal desorption and subsequent GC/MS analysis. The carbonyls identified include formaldehyde, acetaldehyde, acrolein, 2-furfural, benzaldehyde, glyoxal, and methylglyoxal. The levels of the above carbonyls correlate with the intensity of the incense-burning activities. The total mixing ratios of the carbonyls in the temple exceed those in the ambient air outside the temple by 11-23 times. Formaldehyde is the most abundant species, contributing to approximately 55% of the total carbonyl mixing ratios in both the temple and the home environments during incense burning. The mixing ratio of formaldehyde ranges from 108 to 346 ppbv in the temple and averages 103 ppbv in the home during incense burning. These values exceed the World Health Organization (WHO) air quality guideline of 100 microg m(-3) (88 ppbv) for formaldehyde. The highest formaldehyde level in the temple exceeds the WHO guideline by 3 times at peak incense burning hours. The mixing ratio of acrolein in the temple ranges from 20 to 99 ppbv, approaching or exceeding the WHO air quality guideline of 50 microg m(-3) (22 ppbv) for acrolein. Our measurements indicate that incense burning significantly elevates the concentrations of a number of carbonyls, most notably formaldehyde and acrolein, in the surrounding environments. This study provides preliminary insights on indoor air quality problems created by incense burning.

  12. Bioinduced Room-Temperature Methanol Reforming.

    PubMed

    Heim, Leo E; Thiel, Daniel; Gedig, Christian; Deska, Jan; Prechtl, Martin H G

    2015-08-24

    Imitating nature's approach in nucleophile-activated formaldehyde dehydrogenation, air-stable ruthenium complexes proved to be exquisite catalysts for the dehydrogenation of formaldehyde hydrate as well as for the transfer hydrogenation to unsaturated organic substrates at loadings as low as 0.5 mol %. Concatenation of the chemical hydrogen-fixation route with an oxidase-mediated activation of methanol gives an artificial methylotrophic in vitro metabolism providing methanol-derived reduction equivalents for synthetic hydrogenation purposes. Moreover, for the first time methanol reforming at room temperature was achieved on the basis of this bioinduced dehydrogenation path delivering hydrogen gas from aqueous methanol.

  13. Acrolein metabolites, diabetes and insulin resistance.

    PubMed

    Feroe, Aliya G; Attanasio, Roberta; Scinicariello, Franco

    2016-07-01

    Acrolein is a dietary and environmental pollutant that has been associated in vitro to dysregulate glucose transport. We investigated the association of urinary acrolein metabolites N-acetyl-S-(3-hydroxypropyl)-l-cysteine (3-HPMA) and N-acetyl-S-(carboxyethyl)-l-cysteine (CEMA) and their molar sum (∑acrolein) with diabetes using data from investigated 2027 adults who participated in the 2005-2006 National Health and Nutrition Examination Survey (NHANES). After excluding participants taking insulin or other diabetes medication we, further, investigated the association of the compounds with insulin resistance (n=850), as a categorical outcome expressed by the homeostatic model assessment (HOMA-IR>2.6). As secondary analyses, we investigated the association of the compounds with HOMA-IR, HOMA-β, fasting insulin and fasting plasma glucose. The analyses were performed using urinary creatinine as independent variable in the models, and, as sensitivity analyses, the compounds were used as creatinine corrected variables. Diabetes as well as insulin resistance (defined as HOMA-IR>2.6) were positively associated with the 3-HPMA, CEMA and ∑Acrolein with evidence of a dose-response relationship (p<0.05). The highest 3rd and 4th quartiles of CEMA compared to the lowest quartile were significantly associated with higher HOMA-IR, HOMA-β and fasting insulin with a dose-response relationship. The highest 3rd quartile of 3-HPMA and ∑Acrolein were positively and significantly associated with HOMA-IR, HOMA-β and fasting insulin. These results suggest a need of further studies to fully understand the implications of acrolein with type 2 diabetes and insulin. PMID:26991531

  14. Proteomic profiling of rat lung epithelial cells induced by acrolein

    PubMed Central

    Sarkar, Poonam; Hayes, Barbara E.

    2009-01-01

    Aims Acrolein is a highly toxic unsaturated aldehyde and is also an endogenous byproduct produced from lipid peroxidation. It can be formed from the breakdown of certain pollutants in outdoor air or from burning tobacco or gasoline. Inhalation and dermal exposure to acrolein are extremely toxic to human tissue. Although it is known that acrolein is toxic to lung tissue, no studies have attempted to address the changes induced by acrolein on a global scale. Main methods In the present study we have attempted to address the changes in global protein expression induced by acrolein using proteomics analysis in rat lung epithelial cells. Key findings Our analysis reveals a comprehensive profiling of the proteins that includes a heterogeneous class of proteins and this compels one to consider that the toxic response to acrolein is very complex. There were 34 proteins that showed changes between the control cells and after acrolein treatment. The expression of 18 proteins was increased and the expression of 16 proteins was decreased following exposure to acrolein. We have further validated two differentially expressed proteins namely annexin II (ANXII) and prohibitin (PHB) in lung epithelial cells treated with acrolein. Significance Based on the results of the overall proteomic analysis, acrolein appears to induce changes in a diverse range of proteins suggesting a complex mechanism of acrolein-induced toxicity in lung epithelial cells. PMID:19490921

  15. Inactivation of GAPDH as one mechanism of acrolein toxicity.

    PubMed

    Nakamura, Mizuho; Tomitori, Hideyuki; Suzuki, Takehiro; Sakamoto, Akihiko; Terui, Yusuke; Saiki, Ryotaro; Dohmae, Naoshi; Igarashi, Kazuei; Kashiwagi, Keiko

    2013-01-25

    We have recently reported that acrolein is more toxic than reactive oxygen species. Thus, the mechanism of cell toxicity by acrolein was studied using mouse mammary carcinoma FM3A cells. Acrolein-conjugated proteins were separated by gel electrophoresis with subsequent determination of their amino acid sequence, and it was found that glyceraldehyde-3-phosphate dehydrogenase (GAPDH) was one of the major acrolein-conjugated proteins in cells. Acrolein interacted with cysteine-150 at the active site of GAPDH, and also with cysteine-282. When cells were treated with 8 μM acrolein, the activity of acrolein-conjugated GAPDH was greatly reduced, and the ATP content in cells was thus significantly reduced. In addition, it was shown that acrolein-conjugated GAPDH translocated to the nucleus, and the level of acetylated GAPDH and the number of TUNEL positive cells was increased, indicating that cell death is enhanced by acrolein-conjugated GAPDH. Inhibition of cell growth by acrolein was partially reversed when the cDNA encoding GAPDH was transformed into cells. These results indicate that inactivation of GAPDH is one mechanism that underlies cell toxicity caused by acrolein.

  16. Polyamine modification by acrolein exclusively produces 1,5-diazacyclooctanes: a previously unrecognized mechanism for acrolein-mediated oxidative stress.

    PubMed

    Tsutsui, Ayumi; Imamaki, Rie; Kitazume, Shinobu; Hanashima, Shinya; Yamaguchi, Yoshiki; Kaneda, Masato; Oishi, Shinya; Fujii, Nobutaka; Kurbangalieva, Almira; Taniguchi, Naoyuki; Tanaka, Katsunori

    2014-07-28

    Acrolein, a toxic unsaturated aldehyde generated as a result of oxidative stress, readily reacts with a variety of nucleophilic biomolecules. Polyamines, which produced acrolein in the presence of amine oxidase, were then found to react with acrolein to produce 1,5-diazacyclooctane, a previously unrecognized but significant downstream product of oxidative stress. Although diazacyclooctane formation effectively neutralized acrolein toxicity, the diazacyclooctane hydrogel produced through a sequential diazacyclooctane polymerization reaction was highly cytotoxic. This study suggests that diazacyclooctane formation is involved in the mechanism underlying acrolein-mediated oxidative stress.

  17. Health and environmental effects profile for acrolein

    SciTech Connect

    Not Available

    1985-09-01

    The Health and Environmental Effects Profile for acrolein was prepared by the Office of Health and Environmental Assessment, Environmental Criteria and Assessment Office, Cincinnati, OH for the Office of Solid Waste and Emergency Response to support listings of hazardous constituents of a wide range of waste streams under Section 3001 of the Resource Conservation and Recovery Act (RCRA) and to provide health-related limits for emergency actions under Section 101 of the Comprehensive Environmental Response, Compensation and Liability Act (CERCLA). Both published literature and information obtained from Agency program office files were evaluated as they pertained to potential human health, aquatic life, and environmental effects of hazardous-waste constituents. Quantitative estimates are presented, provided sufficient data are available. Acrolein was determined to be a systemic toxicant. An Acceptable Daily Intake (ADI), defined as the amount of a chemical to which humans can be exposed on a daily basis over an extended period of time (usually a lifetime) without suffering a deleterious effect, for acrolein is 1.09 mg/day for oral exposure. The Reportable Quantity (RQ) value of 1, 10, 100, 1000, or 5000 pounds is used to determine the quantity of a hazardous substance for which notification is required in the event of a release as specified by CERCLA based on chronic toxicity. The RQ value for acrolein is 10.

  18. Acrolein and embryogenesis: an experimental study

    SciTech Connect

    Chhibber, G.; Cilani, S.H.

    1986-01-01

    The effects of acrolein were studied on the chick embryos of 48 and 72 hr of incubation. Acrolein was dissolved in physiological saline and injected into the air sacs of the eggs at doses ranging from 0.001 to 0.1 mg per egg. The controls received and equal amount of saline only (0.1 ml per egg). All the embryos including controls were examined at Day 13. In all, 600 eggs were utilized for this investigation. At 48 hr incubation, the percentage survival ranged from 80 to 0 as the dosage of acrolein was increased. Embryonic mortality following 72 hr incubation did not increase significantly at any dose level. Gross malformations such as short and twisted limbs, everted viscera, microphthalmia, short and twisted neck, and hemorrhage over the body were observed. The frequency and the types of gross abnormalities did not vary much in the 48- or 72-hr-treated groups. The incidence of malformation in the controls was low. The results of this study indicates that acrolein is embryotoxic at higher doses and moderately teratogenic to chick embryogenesis.

  19. Protein modification by acrolein: Formation and stability of cysteine adducts

    PubMed Central

    Cai, Jian; Bhatnagar, Aruni; Pierce, William M.

    2010-01-01

    The toxicity of the ubiquitous pollutant and endogenous metabolite, acrolein, is due in part to covalent protein modifications. Acrolein reacts readily with protein nucleophiles via Michael addition and Schiff base formation. Potential acrolein targets in protein include the nucleophilic side chains of cysteine, histidine, and lysine residues as well as the free amino terminus of proteins. Although cysteine is the most acrolein-reactive residue, cysteine-acrolein adducts are difficult to identify in vitro and in vivo. In this study, model peptides with cysteine, lysine, and histidine residues were used to examine the reactivity of acrolein. Results from these experiments show that acrolein reacts rapidly with cysteine residues through Michael addition to form M+56 Da adducts. These M+56 adducts are, however, not stable, even though spontaneous dissociation of the adduct is slow. Further studies demonstrated that when acrolein and model peptides are incubated at physiological pH and temperature, the M+56 adducts decreased gradually accompanied by the increase of M+38 adducts, which are formed from intra-molecular Schiff base formation. Adduct formation with the side chains of other amino acid residues (lysine and histidine) was much slower than cysteine and required higher acrolein concentration. When cysteine residues were blocked by reaction with iodoacetamide and higher concentrations of acrolein were used, adducts of the N-terminal amino group or histidyl residues were formed but lysine adducts were not detected. Collectively, these data demonstrate that acrolein reacts avidly with protein cysteine residues and that the apparent loss of protein-acrolein Michael adducts over time may be related to the appearance of a novel (M+38) adduct. These findings may be important in identification of in vivo adducts of acrolein with protein cysteine residues. PMID:19231900

  20. Exposure to acrolein by inhalation causes platelet activation

    SciTech Connect

    Sithu, Srinivas D.; Srivastava, Sanjay; Siddiqui, Maqsood A.; Vladykovskaya, Elena; Riggs, Daniel W.; Conklin, Daniel J.; Haberzettl, Petra; O'Toole, Timothy E.; Bhatnagar, Aruni; D'Souza, Stanley E.

    2010-10-15

    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 cause 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.

  1. EXPOSURE TO ACROLEIN BY INHALATION CAUSES PLATELET ACTIVATION

    PubMed Central

    Sithu, Srinivas D; Srivastava, Sanjay; Siddiqui, Maqsood A; Vladykovskaya, Elena; Riggs, Daniel W; Conklin, Daniel J; Haberzettl, Petra; O’Toole, Timothy E; Bhatnagar, Aruni; D’Souza, Stanley E

    2010-01-01

    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, 6h/day for 4 days) acrolein inhalation exposures. The acute exposure to acrolein did not cause 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. PMID:20678513

  2. Synthesis of Reactive Polymers for Acrolein Capture Using AGET ATRP.

    PubMed

    Beringer, Laura T; Li, Shaohua; Gilmore, Gary; Lister, John; Averick, Saadyah

    2015-10-01

    Acrolein is a toxic metabolite of the anticancer agent cyclophosphamide (CP). Current strategies to mitigate acrolein toxicity are insufficient, and in this brief article, we report the synthesis of well-defined low molecular weight block copolymers using activators generated by electron transfer atom transfer radical polymerization (AGET ATRP) capable of reacting with the cytotoxic small molecule acrolein. Acrolein reactivity was introduced into the block copolymers via incorporation of either (a) aminooxy or (b) sulfhydryl groups. The cytoprotective effect of the polymers was compared to sodium 2-sulfanylethanesulfonate (mesna) the current gold standard for protection from CP urotoxicity, and we found that the polymers bearing sulfhydryl moieties demonstrated superior cytoprotective activity.

  3. Proteomic analysis of rat cerebral cortex following subchronic acrolein toxicity.

    PubMed

    Rashedinia, Marzieh; Lari, Parisa; Abnous, Khalil; Hosseinzadeh, Hossein

    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 3mg/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 were 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.

  4. Effects of formaldehyde on mitochondrial dysfunction and apoptosis in SK-N-SH neuroblastoma cells.

    PubMed

    Zerin, Tamanna; Kim, Jin-Sun; Gil, Hyo-Wook; Song, Ho-Yeon; Hong, Sae-Yong

    2015-12-01

    Methanol ingestion is neurotoxic in humans due to its metabolites, formaldehyde and formic acid. Here, we compared the cytotoxicity of methanol and its metabolites on different types of cells. While methanol and formic acid did not affect the viability of the cells, formaldehyde (200-800 μg/mL) was strongly cytotoxic in all cell types tested. We investigated the effects of formaldehyde on oxidative stress, mitochondrial respiratory functions, and apoptosis on the sensitive neuronal SK-N-SH cells. Oxidative stress was induced after 2 h of formaldehyde exposure. Formaldehyde at a concentration of 400 μg/mL for 12 h of treatment greatly reduced cellular adenosine triphosphate (ATP) levels. Confocal microscopy indicated that the mitochondrial membrane potential (MMP) was dose-dependently reduced by formaldehyde. A marked and dose-dependent inhibition of mitochondrial respiratory enzymes, viz., NADH dehydrogenase (complex I), cytochrome c oxidase (complex IV), and oxidative stress-sensitive aconitase was also detected following treatment with formaldehyde. Furthermore, formaldehyde caused a concentration-dependent increase in nuclear fragmentation and in the activities of the apoptosis-initiator caspase-9 and apoptosis-effector caspase-3/-7, indicating apoptosis progression. Our data suggests that formaldehyde exerts strong cytotoxicity, at least in part, by inducing oxidative stress, mitochondrial dysfunction, and eventually apoptosis. Changes in mitochondrial respiratory function and oxidative stress by formaldehyde may therefore be critical in methanol-induced toxicity.

  5. Surface complexes of acrolein on oxide catalysts

    SciTech Connect

    Popova, G.Ya.; Davydov, A.A.; Andrushkevich, T.V.; Zakharov, I.I.

    1995-01-01

    It is shown that acrolein can be adsorbed by different mechanisms on the surface of oxide catalysts with the formation of {sigma}- and {pi}-complexes, H-complexes with surface OH groups; a species bound via the carbonyl group (the dissociative form of adsorption); and oxidized fragments, such as surface acrylates, carboxylates, formylacetates, and malonates. On the basis of the quantum-chemical analysis of the acrolein interaction with the surface of oxide catalysts in combination with IR-spectroscopic, thermodesorption, and catalytic studies, a conclusion has been drawn that the formation of a certain surface species and its reactivity are determined by the nature of an adsorption site and by the reactivity of surface oxygen.

  6. Proteomic analysis of rat cerebral cortex following subchronic acrolein toxicity

    SciTech Connect

    Rashedinia, Marzieh; Lari, Parisa; Abnous, Khalil; Hosseinzadeh, Hossein

    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 were 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.

  7. Potential role of acrolein in neurodegeneration and in Alzheimer's disease.

    PubMed

    Dang, Thanh Nam; Arseneault, Madeleine; Murthy, Ven; Ramassamy, Charles

    2010-06-01

    Lipid peroxidation leads to the formation of a number of aldehydes by-products, including acrolein. The most abundant aldehydes are 4-hydroxy-nonenal (4-HNE) and malondialdehyde (MDA) while acrolein is the most reactive. In Alzheimer's brain, acrolein was found to be elevated in hippocampus and temporal cortex where oxidative stress is high. In late onset Alzheimer's disease (AD), a 2-fold increase in levels of acrolein/guanosine adducts in nDNA were isolated from the hippocampus of AD as compared to age-matched control. These adducts are biologically relevant in that they may promote DNA-DNA and DNA-protein cross-linking while 4-HNE/guanosine adduct in nDNA was not elevated in AD. In AD, the activity of the glutathione-S-transferase, the main enzyme responsible for the detoxification of acrolein is significantly decreased in hippocampus. On neuronal primary culture from hippocampus, acrolein caused cell death and its toxicity is higher than 4-hydroxynonenal. Acrolein could modulate tau phosphorylation through different pathways. Acrolein has been shown to inhibit the mitochondrial activity. Due to its high reactivity, acrolein is not only a marker of lipid peroxidation but also an initiator of oxidative stress by adducting cellular nucleophilic groups found on proteins, lipids, and nucleic acid. As a strong electrophile molecule, acrolein can react about 110-150 times faster with the thiol group of cysteine than with 4-hydroxynonenal and decrease the level of the antioxidant glutathione. Taken together, these reactions suggest that acrolein could play a role in the pathophysiology of AD. In this review, we will summarize some mechanisms implicated in the toxicity of this by-product of lipid peroxidation in brain and their implication in AD.

  8. Acrolein-mediated injury in nervous system trauma and diseases

    PubMed Central

    Shi, Riyi; Rickett, Todd; Sun, Wenjing

    2012-01-01

    Acrolein, an α,β-unsaturated aldehyde, is a ubiquitous pollutant that is also produced endogenously through lipid peroxidation. This compound is hundreds of times more reactive than other aldehydes such as 4-hydroxynonenal, is produced at much higher concentrations, and persists in solution for much longer than better known free radicals. It has been implicated in disease states known to involve chronic oxidative stress, particularly spinal cord injury and multiple sclerosis. Acrolein may overwhelm the anti-oxidative systems of any cell by depleting glutathione reserves, preventing glutathione regeneration, and inactivating protective enzymes. On the cellular level, acrolein exposure can cause membrane damage, mitochondrial dysfunction, and myelin disruption. Such pathologies can be exacerbated by increased concentrations or duration of exposure, and can occur in normal tissue incubated with injured spinal cord, showing that acrolein can act as a diffusive agent, spreading secondary injury. Several chemical species are capable of binding and inactivating acrolein. Hydralazine in particular can reduce acrolein concentrations and inhibit acrolein-mediated pathologies in vivo. Acrolein scavenging appears to be a novel effective treatment which is primed for rapid translation to the clinic. PMID:21823221

  9. Methanol test

    MedlinePlus

    ... sources of methanol in the body include fruits, vegetables, and diet drinks that contain aspartame. Methanol is ... eat or drink it in toxic amounts. Methanol poisoning mainly affects the digestive system, nervous system, and ...

  10. Comments on the purported generation of formaldehyde and adduct formation from the sweetener aspartame.

    PubMed

    Tephly, T R

    1999-01-01

    A recent paper by Trocho et al. (1) describes experiments meant to show that formaldehyde adducts are formed when rats are administered the sweetener aspartame. These authors assume that the methanol carbon of aspartame generates formaldehyde which then forms adducts with protein, DNA, and RNA. Doses employed range widely. In this letter, studies which have been published previously and which were not cited by these authors are reviewed in order to put into perspective the disposition of methanol and formaldehyde in monkeys and humans, species relevant to the toxicity of methanol and its toxic metabolite, formic acid.

  11. Molecular Mechanisms of Acrolein Toxicity: Relevance to Human Disease

    PubMed Central

    Moghe, Akshata; Ghare, Smita; Lamoreau, Bryan; Mohammad, Mohammad; Barve, Shirish; McClain, Craig; Joshi-Barve, Swati

    2015-01-01

    Acrolein, a highly reactive unsaturated aldehyde, is a ubiquitous environmental pollutant and its potential as a serious environmental health threat is beginning to be recognized. Humans are exposed to acrolein per oral (food and water), respiratory (cigarette smoke, automobile exhaust, and biocide use) and dermal routes, in addition to endogenous generation (metabolism and lipid peroxidation). Acrolein has been suggested to play a role in several disease states including spinal cord injury, multiple sclerosis, Alzheimer’s disease, cardiovascular disease, diabetes mellitus, and neuro-, hepato-, and nephro-toxicity. On the cellular level, acrolein exposure has diverse toxic effects, including DNA and protein adduction, oxidative stress, mitochondrial disruption, membrane damage, endoplasmic reticulum stress, and immune dysfunction. This review addresses our current understanding of each pathogenic mechanism of acrolein toxicity, with emphasis on the known and anticipated contribution to clinical disease, and potential therapies. PMID:25628402

  12. Molecular mechanisms of acrolein toxicity: relevance to human disease.

    PubMed

    Moghe, Akshata; Ghare, Smita; Lamoreau, Bryan; Mohammad, Mohammad; Barve, Shirish; McClain, Craig; Joshi-Barve, Swati

    2015-02-01

    Acrolein, a highly reactive unsaturated aldehyde, is a ubiquitous environmental pollutant and its potential as a serious environmental health threat is beginning to be recognized. Humans are exposed to acrolein per oral (food and water), respiratory (cigarette smoke, automobile exhaust, and biocide use) and dermal routes, in addition to endogenous generation (metabolism and lipid peroxidation). Acrolein has been suggested to play a role in several disease states including spinal cord injury, multiple sclerosis, Alzheimer's disease, cardiovascular disease, diabetes mellitus, and neuro-, hepato-, and nephro-toxicity. On the cellular level, acrolein exposure has diverse toxic effects, including DNA and protein adduction, oxidative stress, mitochondrial disruption, membrane damage, endoplasmic reticulum stress, and immune dysfunction. This review addresses our current understanding of each pathogenic mechanism of acrolein toxicity, with emphasis on the known and anticipated contribution to clinical disease, and potential therapies.

  13. New formaldehyde base disinfectants.

    NASA Technical Reports Server (NTRS)

    Trujillo, R.; Lindell, K. F.

    1973-01-01

    Preparations of formaldehyde in various organic liquids - ethylene glycol, glycerol, and propylene glycol - serve as effective disinfectants towards microbial vegetative cells and spores. This disinfection is a temperature-dependent process and is manifest when these formaldehyde base disinfectants are dissolved in water. The irritating vapors associated with formaldehyde disinfection are not present in either of these new formaldehyde base disinfectants or in aqueous solutions of them.

  14. Acrolein induction of oxidative stress and degranulation in mast cells.

    PubMed

    Hochman, Daniel J; Collaco, Christopher R; Brooks, Edward G

    2014-08-01

    Increases in asthma worldwide have been associated epidemiologically with expanding urban air pollution. The mechanistic relationship between airway hyper-responsiveness, inflammation, and ambient airborne triggers remains ambiguous. Acrolein, a ubiquitous aldehyde pollutant, is a product of incomplete combustion reactions. Acrolein is abundant in cigarette smoke, effluent from industrial smokestacks, diesel exhaust, and even hot oil cooking vapors. Acrolein is a potent airway irritant and can induce airway hyper-responsiveness and inflammation in the lungs of animal models. In the present study, we utilized the mast cell analog, RBL-2H3, to interrogate the responses of cells relevant to airway inflammation and allergic responses as a model for the induction of asthma-like conditions upon exposure to acrolein. We hypothesized that acrolein would induce oxidative stress and degranulation in airway mast cells. Our results indicate that acrolein at 1 ppm initiated degranulation and promoted the generation of reactive oxygen species (ROS). Introduction of antioxidants to the system significantly reduced both ROS generation and degranulation. At higher levels of exposure (above 100 ppm), RBL-2H3 cells displayed signs of severe toxicity. This experimental data indicates acrolein can induce an allergic inflammation in mast cell lines, and the initiation of degranulation was moderated by the application of antioxidants.

  15. Acrolein Consumption Induces Systemic Dyslipidemia and Lipoprotein Modification

    PubMed Central

    Conklin, Daniel J.; Barski, Oleg A.; Lesgards, Jean-Francois; Juvan, Peter; Rezen, Tadeja; Rozman, Damjana; Prough, Russell A.; Vladykovskaya, Elena; Liu, SiQi; Srivastava, Sanjay; Bhatnagar, Aruni

    2010-01-01

    Aldehydes such as acrolein are ubiquitous pollutants present in automobile exhaust, cigarette, wood, and coal smoke. Such aldehydes are also constituents of several food substances and are present in drinking water, irrigation canals, and effluents from manufacturing plants. Oral intake represents the most significant source of exposure to acrolein and related aldehydes. To study the effects of short-term oral exposure to acrolein on lipoprotein levels and metabolism, adult mice were gavage fed 0.1 to 5 mg acrolein/kg bwt and changes in plasma lipoproteins were assessed. Changes in hepatic gene expression related to lipid metabolism and cytokines were examined by qRT-PCR analysis. Acrolein feeding did not affect body weight, BUN, plasma creatinine, electrolytes, cytokines or liver enzymes, but increased plasma cholesterol and triglycerides. Similar results were obtained with apoE-null mice. Plasma lipoproteins from acrolein-fed mice showed altered electrophoretic mobility on agarose gels. Chromatographic analysis revealed elevated VLDL cholesterol, phospholipids, and triglycerides levels with little change in LDL or HDL. NMR analysis indicated shifts from small to large VLDL and from large to medium-small LDL with no change in the size of HDL particles. Increased plasma VLDL was associated with a significant decrease in post-heparin plasma hepatic lipase activity and a decrease in hepatic expression of hepatic lipase. These observations suggest that oral exposure to acrolein could induce or exacerbate systemic dyslipidemia and thereby contribute to cardiovascular disease risk. PMID:20034506

  16. Acrolein consumption induces systemic dyslipidemia and lipoprotein modification

    SciTech Connect

    Conklin, Daniel J.; Barski, Oleg A.; Lesgards, Jean-Francois; Juvan, Peter; Rezen, Tadeja; Rozman, Damjana; Prough, Russell A.; Vladykovskaya, Elena; Liu, SiQi; Srivastava, Sanjay; Bhatnagar, Aruni

    2010-02-15

    Aldehydes such as acrolein are ubiquitous pollutants present in automobile exhaust, cigarette, wood, and coal smoke. Such aldehydes are also constituents of several food substances and are present in drinking water, irrigation canals, and effluents from manufacturing plants. Oral intake represents the most significant source of exposure to acrolein and related aldehydes. To study the effects of short-term oral exposure to acrolein on lipoprotein levels and metabolism, adult mice were gavage-fed 0.1 to 5 mg acrolein/kg bwt and changes in plasma lipoproteins were assessed. Changes in hepatic gene expression related to lipid metabolism and cytokines were examined by qRT-PCR analysis. Acrolein feeding did not affect body weight, blood urea nitrogen, plasma creatinine, electrolytes, cytokines or liver enzymes, but increased plasma cholesterol and triglycerides. Similar results were obtained with apoE-null mice. Plasma lipoproteins from acrolein-fed mice showed altered electrophoretic mobility on agarose gels. Chromatographic analysis revealed elevated VLDL cholesterol, phospholipids, and triglycerides levels with little change in LDL or HDL. NMR analysis indicated shifts from small to large VLDL and from large to medium-small LDL with no change in the size of HDL particles. Increased plasma VLDL was associated with a significant decrease in post-heparin plasma hepatic lipase activity and a decrease in hepatic expression of hepatic lipase. These observations suggest that oral exposure to acrolein could induce or exacerbate systemic dyslipidemia and thereby contribute to cardiovascular disease risk.

  17. Protein-bound acrolein: Potential markers for oxidative stress

    PubMed Central

    Uchida, Koji; Kanematsu, Masamichi; Sakai, Kensuke; Matsuda, Tsukasa; Hattori, Nobutaka; Mizuno, Yoshikuni; Suzuki, Daisuke; Miyata, Toshio; Noguchi, Noriko; Niki, Etsuo; Osawa, Toshihiko

    1998-01-01

    Acrolein (CH2=CH—CHO) is known as a ubiquitous pollutant in the environment. Here we show that this notorious aldehyde is not just a pollutant, but also a lipid peroxidation product that could be ubiquitously generated in biological systems. Upon incubation with BSA, acrolein was rapidly incorporated into the protein and generated the protein-linked carbonyl derivative, a putative marker of oxidatively modified proteins under oxidative stress. To verify the presence of protein-bound acrolein in vivo, the mAb (mAb5F6) against the acrolein-modified keyhole limpet hemocyanin was raised. It was found that the acrolein-lysine adduct, Nɛ-(3-formyl-3,4-dehydropiperidino)lysine, constitutes an epitope of the antibody. Immunohistochemical analysis of atherosclerotic lesions from a human aorta demonstrated that antigenic materials recognized by mAb5F6 indeed constituted the lesions, in which intense positivity was associated primarily with macrophage-derived foam cells and the thickening neointima of arterial walls. The observations that (i) oxidative modification of low-density lipoprotein with Cu2+ generated the acrolein-low-density lipoprotein adducts and (ii) the iron-catalyzed oxidation of arachidonate in the presence of protein resulted in the formation of antigenic materials suggested that polyunsaturated fatty acids are sources of acrolein that cause the production of protein-bound acrolein. These data suggest that the protein-bound acrolein represents potential markers of oxidative stress and long-term damage to protein in aging, atherosclerosis, and diabetes. PMID:9560197

  18. Conjugation vs hyperconjugation in molecular structure of acrolein

    NASA Astrophysics Data System (ADS)

    Shishkina, Svitlana V.; Slabko, Anzhelika I.; Shishkin, Oleg V.

    2013-01-01

    Analysis of geometric parameters of butadiene and acrolein reveals the contradiction between the Csp2-Csp2 bond length in acrolein and classical concept of conjugation degree in the polarized molecules. In this Letter the reasons of this contradiction have been investigated. It is concluded that the Csp2-Csp2 bond length in acrolein is determined by influence of the bonding for it π-π conjugation and antibonding n → σ∗ hyperconjugation between the oxygen lone pair and the antibonding orbital of the single bond. It was shown also this bond length depends on the difference in energy of conjugative and hyperconjugative interactions.

  19. Acrolein-mediated conduction loss is partially restored by K⁺ channel blockers.

    PubMed

    Yan, Rui; Page, Jessica C; Shi, Riyi

    2016-02-01

    Acrolein-mediated myelin damage is thought to be a critical mechanism leading to conduction failure following neurotrauma and neurodegenerative diseases. The exposure and activation of juxtaparanodal voltage-gated K(+) channels due to myelin damage leads to conduction block, and K(+) channel blockers have long been studied as a means for restoring axonal conduction in spinal cord injury (SCI) and multiple sclerosis (MS). In this study, we have found that 100 μM K(+) channel blockers 4-aminopyridine-3-methanol (4-AP-3-MeOH), and to a lesser degree 4-aminopyridine (4-AP), can significantly restore compound action potential (CAP) conduction in spinal cord tissue following acrolein-mediated myelin damage using a well-established ex vivo SCI model. In addition, 4-AP-3-MeOH can effectively restore CAP conduction in acrolein-damaged axons with a range of concentrations from 0.1 to 100 μM. We have also shown that while both compounds at 100 μM showed no preference of small- and large-caliber axons when restoring CAP conduction, 4-AP-3-MeOH, unlike 4-AP, is able to augment CAP amplitude while causing little change in axonal responsiveness measured in refractory periods and response to repetitive stimuli. In a prior study, we show that 4-AP-3-MeOH was able to functionally rescue mechanically injured axons. In this investigation, we conclude that 4-AP-3-MeOH is an effective K(+) channel blocker in restoring axonal conduction following both primary (physical) and secondary (chemical) insults. These findings also suggest that 4-AP-3-MeOH is a viable alternative of 4-AP for treating myelin damage and improving function following central nervous system trauma and neurodegenerative diseases. PMID:26581866

  20. Acrolein-mediated conduction loss is partially restored by K⁺ channel blockers.

    PubMed

    Yan, Rui; Page, Jessica C; Shi, Riyi

    2016-02-01

    Acrolein-mediated myelin damage is thought to be a critical mechanism leading to conduction failure following neurotrauma and neurodegenerative diseases. The exposure and activation of juxtaparanodal voltage-gated K(+) channels due to myelin damage leads to conduction block, and K(+) channel blockers have long been studied as a means for restoring axonal conduction in spinal cord injury (SCI) and multiple sclerosis (MS). In this study, we have found that 100 μM K(+) channel blockers 4-aminopyridine-3-methanol (4-AP-3-MeOH), and to a lesser degree 4-aminopyridine (4-AP), can significantly restore compound action potential (CAP) conduction in spinal cord tissue following acrolein-mediated myelin damage using a well-established ex vivo SCI model. In addition, 4-AP-3-MeOH can effectively restore CAP conduction in acrolein-damaged axons with a range of concentrations from 0.1 to 100 μM. We have also shown that while both compounds at 100 μM showed no preference of small- and large-caliber axons when restoring CAP conduction, 4-AP-3-MeOH, unlike 4-AP, is able to augment CAP amplitude while causing little change in axonal responsiveness measured in refractory periods and response to repetitive stimuli. In a prior study, we show that 4-AP-3-MeOH was able to functionally rescue mechanically injured axons. In this investigation, we conclude that 4-AP-3-MeOH is an effective K(+) channel blocker in restoring axonal conduction following both primary (physical) and secondary (chemical) insults. These findings also suggest that 4-AP-3-MeOH is a viable alternative of 4-AP for treating myelin damage and improving function following central nervous system trauma and neurodegenerative diseases.

  1. Catalytic reaction of acrolein and methacrolein with alcohols and glycols

    SciTech Connect

    Paparizos, C.; shout, R. S.; Shaw, W. G.

    1985-02-12

    Disclosed is the reaction acrolein or methacrolein with a mono- or dihydroxyalkane to produce a 3-alkoxypropionaldehyde or a 3-(hydroxyalkoxy)propionaldehyde in the case of acrolein; or to produce a 3-alkoxy-2-methylpropionaldehyde or a 3-(hydroxyalkoxy)-2-methylpropionaldehyde in the case of methacrolein, by contacting a mixture of the recited reactants with a particulate solid metallic catalyst comprising an alloy of palladium and cadmium.

  2. Acrolein stimulates eicosanoid release from bovine airway epithelial cells

    SciTech Connect

    Doupnik, C.A.; Leikauf, G.D. )

    1990-10-01

    Injury to the airway mucosa after exposure to environmental irritants is associated with pulmonary inflammation and bronchial hyperresponsiveness. To better understand the relationships between mediator release and airway epithelial cell injury during irritant exposures, we studied the effects of acrolein, a low-molecular-weight aldehyde found in cigarette smoke, on arachidonic acid metabolism in cultured bovine tracheal epithelial cells. Confluent airway epithelial cell monolayers, prelabeled with (3H)arachidonic acid, released significant levels of 3H activity when exposed (20 min) to 100 microM acrolein. (3H)arachidonic acid products were resolved using reverse-phase high-performance liquid chromatography. Under control conditions the released 3H activity coeluted predominantly with the cyclooxygenase product, prostaglandin (PG) E2. After exposure to acrolein, significant peaks in 3H activity coeluted with the lipoxygenase products 12-hydroxyeicosatetraenoic acid (HETE) and 15-HETE, as well as with PGE2, PGF2 alpha, and 6-keto-PGF1 alpha. Dose-response relationships for acrolein-induced release of immunoreactive PGF2 alpha and PGE2 from unlabeled epithelial monolayers demonstrated 30 microM acrolein as the threshold dose, with 100 microM acrolein inducing nearly a fivefold increase in both PGF2 alpha and PGE2. Cellular viability after exposure to 100 microM acrolein, determined by released lactate dehydrogenase activity, was not affected until exposure periods were greater than or equal to 2 h. These results implicate the airway epithelial cell as a possible source of eicosanoids after exposure to acrolein.

  3. [Formaldehyde in hair shampoos].

    PubMed

    Bork, K; Heise, D; Rosinus, A

    1979-01-01

    In most hair shampoos commercially available in Western Germany formaldehyde or formaldehyde liberating substances serve as efficient preservatives especially in shampoos of the lower price group. Besides, PHB-ester, mercury containing substances and since recently brome compounds are used for this purpose. We observed a 15 year old patient who developed an allergic contact dermatitis from formaldehyde in a hair shampoo. However, compared to the widespread opportunities of exposure allergic contact dermatitis caused by hair shampoos is not very frequent. For this rarity of formaldehyde dermatitis caused by shampoos the short period of application and the low concentration because of the high dilution and perhaps the low contact dermatitis reactivity of the scalp are responsible. After all only two out of thirtyone thoroughly questioned patients, who had acquired a professional formaldehyde sensitivity elsewhere, reported a contact dermatitis caused by shampoos, which by the way appeared in the orbital region as typical. Probably allergic contact dermatitis from formaldehyde in shampoos will be expected in patients with a formaldehyde sensitivity acquired formerly elsewhere, especially professionally. To those patients formaldehyde free hair shampoos should be recommended. The declaration of formaledehyde in cosmetics, which will be legally obligatory in Germany in 1979, will be valuable for finding out the alternate products free of formaldehyde.

  4. Acrolein environmental levels and potential for human exposure.

    PubMed

    Faroon, O; Roney, N; Taylor, J; Ashizawa, A; Lumpkin, M H; Plewak, D J

    2008-09-01

    This article provides environmental information on acrolein including environmental fate, potential for human exposure, analytical methods, and a listing of regulations and advisories. Acrolein may be released to the environment in emissions and effluents from its manufacturing and use facilities, in emissions from combustion processes (including cigarette smoking and combustion of petrochemical fuels), from direct application to water and waste water as a slimicide and aquatic herbicide, as a photooxidation product of various hydrocarbon pollutants found in air (including propylene and 1,3-butadiene), and from land disposal of some organic waste materials. Acrolein is a reactive compound and is unstable in the environment. The general population may be exposed to acrolein through inhalation of contaminated air and through ingestion of certain foods. Important sources of acrolein exposure are via inhalation of tobacco smoke and environmental tobacco smoke and via the overheating of fats contained in all living matter. There is potential for exposure to acrolein in many occupational settings as the result of its varied uses and its formation during the combustion and pyrolysis of materials such as wood, petrochemical fuels, and plastics. PMID:19039083

  5. Synthetic smoke with acrolein but not HCl produces pulmonary edema

    SciTech Connect

    Hales, C.A.; Barkin, P.W.; Jung, W.; Trautman, E.; Lamborghini, D.; Herrig, N.; Burke, J.

    1988-03-01

    The chemical toxins in smoke and not the heat are responsible for the pulmonary edema of smoke inhalation. We developed a synthetic smoke composed of carbon particles (mean diameter of 4.3 microns) to which toxins known to be in smoke, such as HCl or acrolein, could be added one at a time. We delivered synthetic smoke to dogs for 10 min and monitored extravascular lung water (EVLW) accumulation thereafter with a double-indicator thermodilution technique. Final EVLW correlated highly with gravimetric values (r = 0.93, P less than 0.01). HCl in concentrations of 0.1-6 N when added to heated carbon (120 degrees C) and cooled to 39 degrees C produced airway damage but no pulmonary edema. Acrolein, in contrast, produced airway damage but also pulmonary edema, whereas capillary wedge pressures remained stable. Low-dose acrolein smoke (less than 200 ppm) produced edema in two of five animals with a 2- to 4-h delay. Intermediate-dose acrolein smoke (200-300 ppm) always produced edema at an average of 147 +/- 57 min after smoke, whereas high-dose acrolein (greater than 300 ppm) produced edema at 65 +/- 16 min after smoke. Thus acrolein but not HCl, when presented as a synthetic smoke, produced a delayed-onset, noncardiogenic, and peribronchiolar edema in a roughly dose-dependent fashion.

  6. Optical detection of formaldehyde

    NASA Astrophysics Data System (ADS)

    Patty, Kira D.; Gregory, Don A.

    2008-04-01

    The potential for buildup of formaldehyde in closed space environments poses a direct health hazard to personnel. The National Aeronautic Space Agency (NASA) has established a maximum permitted concentration of 0.04 ppm for 7 to 180 days for all space craft. Early detection is critical to ensure that formaldehyde levels do not accumulate above these limits. New sensor technologies are needed to enable real time, in situ detection in a compact and reusable form factor. Addressing this need, research into the use of reactive fluorescent dyes which reversibly bind to formaldehyde (liquid or gas) has been conducted to support the development of a formaldehyde sensor. In the presence of formaldehyde the dyes' characteristic fluorescence peaks shift providing the basis for an optical detection. Dye responses to formaldehyde exposure were characterized; demonstrating the optical detection of formaldehyde in under 10 seconds and down to concentrations of 0.5 ppm. To incorporate the dye in an optical sensor device requires a means of containing and manipulating the dye. Multiple form factors using two dissimilar substrates were considered to determine a suitable configuration. A prototype sensor was demonstrated and considerations for a fieldable sensor were presented. This research provides a necessary first step toward the development of a compact, reusable, real time optical formaldehyde sensor suitable for use in the U.S. space program.

  7. Melamine-formaldehyde aerogels

    DOEpatents

    Pekala, Richard W.

    1992-01-01

    Organic aerogels that are transparent and essentially colorless are prepa from the aqueous, sol-gel polymerization of melamine with formaldehyde. The melamine-formaldehyde (MF) aerogels have low densities, high surface areas, continuous porsity, ultrafine cell/pore sizes, and optical clarity.

  8. Melamine-formaldehyde aerogels

    SciTech Connect

    Pekala, R.W.

    1992-01-14

    Organic aerogels that are transparent and essentially colorless are prepared from the aqueous, sol-gel polymerization of melamine with formaldehyde. The melamine-formaldehyde (MF) aerogels have low densities, high surface areas, continuous porosity, ultrafine cell/pore sizes, and optical clarity. 3 figs.

  9. Formaldehyde in Our Environment.

    ERIC Educational Resources Information Center

    Ojanlatva, Ansa; Weeks, Charlie A.

    During the energy crisis of the early 1970s, there was a drive to conserve energy in every segment of society. Citizens were encouraged to insulate their homes and tighten them up to avoid loss of energy. One of the products to emerge from this crisis was urea formaldehyde foam insulation. (Urea formaldehyde is a well-known agent for preserving…

  10. Optical Detection of Formaldehyde

    NASA Technical Reports Server (NTRS)

    Patty, Kira D.; Gregory, Don A.

    2008-01-01

    The potential for buildup .of formaldehyde in closed space environments poses a direct health hazard to personnel. The National Aeronautic Space Agency (NASA) has established a maximum permitted concentration of 0.04 ppm for 7 to 180 days for all space craft. Early detection is critical to ensure that formaldehyde levels do not accumulate. above these limits. New sensor technologies are needed to enable real time,in situ detection in a compact and reusable form factor. Addressing this need,research into the use of reactive fluorescent dyes which reversibly bind to formaldehyde (liquid or gas) has been conducted to support the development of a formaldehyde.sensor. In the presence of formaldehyde the dyes' characteristic fluorescence peaks shift providing the basis for an optical detection. Dye responses to formaldehyde exposure were characterized; demonstrating the optical detection of formaldehyde in under 10 seconds and down to concentrations of 0.5 ppm. To .incorporate the dye .in.an optical sensor device requires. a means of containing and manipulating the dye. Multiple form factors using two dissimilar sbstrates were considered to determine a suitable configuration. A prototype sensor was demonstrated and considerations for a field able sensor were presented. This research provides a necessary first step toward the development of a compact, reusable; real time optical formaldehyde sensor suitable for use in the U.S. space program,

  11. Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

    PubMed

    Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

    2016-05-18

    PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

  12. The formaldehyde dilemma.

    PubMed

    Salthammer, Tunga

    2015-06-01

    The IARC's 2004 classification of formaldehyde as a human carcinogen has led to intensive discussion on scientific and regulatory levels. In June 2014, the European Union followed and classified formaldehyde as a cause of cancer. This automatically triggers consequences in terms of emission minimization and the health-related assessment of building and consumer products. On the other hand, authorities are demanding and authorizing technologies and products which can release significant quantities of formaldehyde into the atmosphere. In the outdoor environment, this particularly applies to combusting fuels. The formation of formaldehyde through photochemical smog has also been a recognized problem for years. Indoors there are various processes which can contribute to increased formaldehyde concentrations. Overall, legislation faces a dilemma: primary sources are often over-regulated while a lack of consideration of secondary sources negates the regulations' effects.

  13. Microbial Formaldehyde Oxidation

    SciTech Connect

    Timothy J. Donohue

    2004-12-09

    This project analyzed how cells sense and generate energy from formaldehyde oxidation. Formaldehyde is a toxin that is produced naturally, chemically or by metabolism of a wide variety of methyl-containing compounds. Our goals are to identify how cells sense the presence of this toxic compound and determine how they generate energy and nutrients from the oxidation of formaldehyde. This research capitalizes on the role of the Rhodobacter sphaeroides glutathione dependent formaldehyde dehydrogenase (GSH FDH) in a formaldehyde oxidation pathway that is apparently found in a wide variety of microbes, plants and animals. Thus, our findings illustrate what is required for a large variety of cells to metabolize this toxic compound. A second major focus of our research is to determine how cells sense the presence of this toxic compound and control the expression of gene products required for its detoxification.

  14. The formaldehyde dilemma.

    PubMed

    Salthammer, Tunga

    2015-06-01

    The IARC's 2004 classification of formaldehyde as a human carcinogen has led to intensive discussion on scientific and regulatory levels. In June 2014, the European Union followed and classified formaldehyde as a cause of cancer. This automatically triggers consequences in terms of emission minimization and the health-related assessment of building and consumer products. On the other hand, authorities are demanding and authorizing technologies and products which can release significant quantities of formaldehyde into the atmosphere. In the outdoor environment, this particularly applies to combusting fuels. The formation of formaldehyde through photochemical smog has also been a recognized problem for years. Indoors there are various processes which can contribute to increased formaldehyde concentrations. Overall, legislation faces a dilemma: primary sources are often over-regulated while a lack of consideration of secondary sources negates the regulations' effects. PMID:25772784

  15. Methanol in dark clouds.

    PubMed

    Friberg, P; Madden, S C; Hjalmarson, A; Irvine, W M

    1988-01-01

    We report observations, for the first time, of the 2(0) - 1(0)A+ and E, 2(-1) - 1(-1) E, and 1(0) - 0(0)A+ lines of methanol (CH3OH) in three dark cold clouds, TMC1, L134N, and B335. The CH3OH emission is extended in these clouds and shows a complex velocity structure. Clear indications of non LTE excitation are observed in TMC 1. Estimated column densities are a few 10(13) cm-2. Although less abundant than formaldehyde (H2CO), methanol is almost an order of magnitude more abundant than acetaldehyde (CH3CHO), in these clouds. Dimethyl ether was searched for in L134N, to an upper limit of 4 10(12) cm-2 (3 sigma). Implications for dark cloud excitation and chemistry are discussed. A new, more accurate, rest frequency 96741.39(0.01) MHz is determined for the 2(0) - 1(0) A+ E line of methanol.

  16. Alzheimer's disease and methanol toxicity (part 1): chronic methanol feeding led to memory impairments and tau hyperphosphorylation in mice.

    PubMed

    Yang, Meifeng; Lu, Jing; Miao, Junye; Rizak, Joshua; Yang, Jianzhen; Zhai, Rongwei; Zhou, Jun; Qu, Jiagui; Wang, Jianhong; Yang, Shangchuan; Ma, Yuanye; Hu, Xintian; He, Rongqiao

    2014-01-01

    Although methanol toxicity is well known for acute neurological sequelae leading to blindness or death, there is a new impetus to investigate the chronic effects of methanol exposure. These include a recently established link between formaldehyde, a methanol metabolite, and Alzheimer's disease (AD) pathology. In the present study, mice were fed with methanol to revisit the chronic effects of methanol toxicity, especially as it pertains to AD progression. Three groups of mice (n = 9) were given either water as a control or a methanol solution (concentrations of 2% or 3.8%) over a 6-week period. The methanol-fed mice were found to have impaired spatial recognition and olfactory memory in Y-maze and olfactory memory paradigms. Immunohistochemical analysis of the mouse brains found increased neuronal tau phosphorylation in the hippocampus and an increased cellular apoptotic marker in hippocampal CA1 neurons (~10% of neurons displayed chromatin condensation) in the methanol-fed groups. Two additional in vitro experiments in mouse embryonic cerebral cortex neurons and mouse neuroblastoma N2a cells found that formaldehyde, but not methanol or the methanol end product formic acid, induced microtubule disintegration and tau protein hyperphosphorylation. The findings of the behavioral tests and immunohistochemical analysis suggested that the methanol-fed mice presented with partial AD-like symptoms. The in vitro experiments suggested that formaldehyde was most likely the detrimental component of methanol toxicity related to hippocampal tau phosphorylation and the subsequent impaired memory in the mice. These findings add to a growing body of evidence that links formaldehyde to AD pathology.

  17. Vocal fold ion transport and mucin expression following acrolein exposure.

    PubMed

    Levendoski, Elizabeth Erickson; Sivasankar, M Preeti

    2014-05-01

    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 (MUC) 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-min 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 MUC 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.

  18. Acrolein impairs the cholesterol transport functions of high density lipoproteins.

    PubMed

    Chadwick, Alexandra C; Holme, Rebecca L; Chen, Yiliang; Thomas, Michael J; Sorci-Thomas, Mary G; Silverstein, Roy L; Pritchard, Kirkwood A; Sahoo, Daisy

    2015-01-01

    High density lipoproteins (HDL) are considered athero-protective, primarily due to their role in reverse cholesterol transport, where they transport cholesterol from peripheral tissues to the liver for excretion. The current study was designed to determine the impact of HDL modification by acrolein, a highly reactive aldehyde found in high abundance in cigarette smoke, on the cholesterol transport functions of HDL. HDL was chemically-modified with acrolein and immunoblot and mass spectrometry analyses confirmed apolipoprotein crosslinking, as well as acrolein adducts on apolipoproteins A-I and A-II. The ability of acrolein-modified HDL (acro-HDL) to serve as an acceptor of free cholesterol (FC) from COS-7 cells transiently expressing SR-BI was significantly decreased. Further, in contrast to native HDL, acro-HDL promotes higher neutral lipid accumulation in murine macrophages as judged by Oil Red O staining. The ability of acro-HDL to mediate efficient selective uptake of HDL-cholesteryl esters (CE) into SR-BI-expressing cells was reduced compared to native HDL. Together, the findings from our studies suggest that acrolein modification of HDL produces a dysfunctional particle that may ultimately promote atherogenesis by impairing functions that are critical in the reverse cholesterol transport pathway.

  19. Microfabricated Formaldehyde Gas Sensors

    PubMed Central

    Flueckiger, Jonas; Ko, Frank K.; Cheung, Karen C.

    2009-01-01

    Formaldehyde is a volatile organic compound that is widely used in textiles, paper, wood composites, and household materials. Formaldehyde will continuously outgas from manufactured wood products such as furniture, with adverse health effects resulting from prolonged low-level exposure. New, microfabricated sensors for formaldehyde have been developed to meet the need for portable, low-power gas detection. This paper reviews recent work including silicon microhotplates for metal oxide-based detection, enzyme-based electrochemical sensors, and nanowire-based sensors. This paper also investigates the promise of polymer-based sensors for low-temperature, low-power operation. PMID:22291561

  20. Metabolic Engineering of Corynebacterium glutamicum for Methanol Metabolism

    PubMed Central

    Witthoff, Sabrina; Schmitz, Katja; Niedenführ, Sebastian; Nöh, Katharina; Noack, Stephan

    2015-01-01

    Methanol is already an important carbon feedstock in the chemical industry, but it has found only limited application in biotechnological production processes. This can be mostly attributed to the inability of most microbial platform organisms to utilize methanol as a carbon and energy source. With the aim to turn methanol into a suitable feedstock for microbial production processes, we engineered the industrially important but nonmethylotrophic bacterium Corynebacterium glutamicum toward the utilization of methanol as an auxiliary carbon source in a sugar-based medium. Initial oxidation of methanol to formaldehyde was achieved by heterologous expression of a methanol dehydrogenase from Bacillus methanolicus, whereas assimilation of formaldehyde was realized by implementing the two key enzymes of the ribulose monophosphate pathway of Bacillus subtilis: 3-hexulose-6-phosphate synthase and 6-phospho-3-hexuloisomerase. The recombinant C. glutamicum strain showed an average methanol consumption rate of 1.7 ± 0.3 mM/h (mean ± standard deviation) in a glucose-methanol medium, and the culture grew to a higher cell density than in medium without methanol. In addition, [13C]methanol-labeling experiments revealed labeling fractions of 3 to 10% in the m + 1 mass isotopomers of various intracellular metabolites. In the background of a C. glutamicum Δald ΔadhE mutant being strongly impaired in its ability to oxidize formaldehyde to CO2, the m + 1 labeling of these intermediates was increased (8 to 25%), pointing toward higher formaldehyde assimilation capabilities of this strain. The engineered C. glutamicum strains represent a promising starting point for the development of sugar-based biotechnological production processes using methanol as an auxiliary substrate. PMID:25595770

  1. Metabolic engineering of Corynebacterium glutamicum for methanol metabolism.

    PubMed

    Witthoff, Sabrina; Schmitz, Katja; Niedenführ, Sebastian; Nöh, Katharina; Noack, Stephan; Bott, Michael; Marienhagen, Jan

    2015-03-01

    Methanol is already an important carbon feedstock in the chemical industry, but it has found only limited application in biotechnological production processes. This can be mostly attributed to the inability of most microbial platform organisms to utilize methanol as a carbon and energy source. With the aim to turn methanol into a suitable feedstock for microbial production processes, we engineered the industrially important but nonmethylotrophic bacterium Corynebacterium glutamicum toward the utilization of methanol as an auxiliary carbon source in a sugar-based medium. Initial oxidation of methanol to formaldehyde was achieved by heterologous expression of a methanol dehydrogenase from Bacillus methanolicus, whereas assimilation of formaldehyde was realized by implementing the two key enzymes of the ribulose monophosphate pathway of Bacillus subtilis: 3-hexulose-6-phosphate synthase and 6-phospho-3-hexuloisomerase. The recombinant C. glutamicum strain showed an average methanol consumption rate of 1.7 ± 0.3 mM/h (mean ± standard deviation) in a glucose-methanol medium, and the culture grew to a higher cell density than in medium without methanol. In addition, [(13)C]methanol-labeling experiments revealed labeling fractions of 3 to 10% in the m + 1 mass isotopomers of various intracellular metabolites. In the background of a C. glutamicum Δald ΔadhE mutant being strongly impaired in its ability to oxidize formaldehyde to CO2, the m + 1 labeling of these intermediates was increased (8 to 25%), pointing toward higher formaldehyde assimilation capabilities of this strain. The engineered C. glutamicum strains represent a promising starting point for the development of sugar-based biotechnological production processes using methanol as an auxiliary substrate.

  2. Current status of acrolein as a lipid peroxidation product.

    PubMed

    Uchida, K

    1999-07-01

    There is increasing evidence that aldehydes generated endogenously during lipid peroxidation contribute to the pathophysiologic effects associated with oxidative stress in cells and tissues. A number of reactive lipid aldehydes, such as 4-hydroxy-2-alkenals and malondialdehyde, have been implicated as causative agents in cytotoxic processes initiated by the exposure of biologic systems to oxidizing agents. Recently, acrolein (CH2 = CH-CHO), a ubiquitous pollutant in the environment, was identified as a product of lipid peroxidation reactions. The basis for this finding is an experimental approach that provides a measure of acrolein bound to lysine residues of protein. The identification of acrolein as an endogenous lipid-derived product suggests an examination of the possible role of this aldehyde as a mediator of oxidative damage in a variety of human diseases.

  3. Anti-acrolein treatment improves behavioral outcome and alleviates myelin damage in EAE mouse

    PubMed Central

    Leung, Gary; Sun, Wenjing; Zheng, Lingxing; Brookes, Sarah; Tully, Melissa; Shi, Riyi

    2011-01-01

    Oxidative stress is considered a major contributor in the pathology of multiple sclerosis (MS). Acrolein, a highly reactive aldehyde byproduct of lipid peroxidation, is thought to perpetuate oxidative stress. In this study, we aimed to determine the role of acrolein in an animal model of MS, experimental autoimmune enchephalomyelitis (EAE) mice. We have demonstrated a significant elevation of acrolein protein adduct levels in EAE mouse spinal cord. Hydralazine, a known acrolein scavenger, significantly improved behavioral outcomes and lessened myelin damage in spinal cord. We postulate that acrolein is an important pathological factor and likely a novel therapeutic target in MS. PMID:21081153

  4. Hydralazine rescues PC12 cells from acrolein-mediated death.

    PubMed

    Liu-Snyder, Peishan; Borgens, Richard Ben; Shi, Riyi

    2006-07-01

    Acrolein, a major lipid peroxidation product, has been associated with both CNS trauma and neurodegenerative diseases. Because of its long half-life, acrolein is a potent endogenous toxin capable of killing healthy cells during the secondary injury process. Traditionally, attempts to intervene in the process of progressive cell death after the primary injury have included scavenging reactive oxygen species (so-called free radicals). The animal data supporting such an approach have generally been positive, but all human clinical trials attempting a similar outcome in human CNS injury have failed. New drugs that might reduce toxicity by scavenging the products of lipid peroxidation present a promising, and little investigated, therapeutic approach. Hydralazine, a well-known treatment for hypertension, has been reported to react with acrolein, forming hydrazone in cell-free systems. In the companion paper, we have established an acrolein-mediated cell injury model using PC12 cells in vitro. Here we test the hypothesis that the formation of hydrazone adducts with acrolein is able to reduce acrolein toxicity and spare a significant percentage of the population of PC12 cells from death. Concentrations of approximately 1 mM of this aldehyde scavenger can rescue over 80% of the population of PC12 cells. This study provides a basis for a new pharmacological treatment to reduce the effects of secondary injury in the damaged and/or diseased nervous system. In particular, we describe the need for new drugs that possess aldehyde scavenging properties but do not interfere with the regulation of blood pressure.

  5. Acute effects of acrolein in human volunteers during controlled exposure

    PubMed Central

    Dwivedi, Aishwarya M.; Johanson, Gunnar; Lorentzen, Johnny C.; Palmberg, Lena; Sjögren, Bengt; Ernstgård, Lena

    2015-01-01

    Abstract Context: Acrolein is a reactive aldehyde mainly formed by combustion. The critical effect is considered to be irritation of the eyes and airways; however, the scarce data available make it difficult to assess effect levels. Objective: The aim of the study was to determine thresholds for acute irritation for acrolein. Methods: Nine healthy volunteers of each sex were exposed at six occasions for 2 h at rest to: clean air, 15 ppm ethyl acetate (EA), and 0.05 ppm and 0.1 ppm acrolein with and without EA (15 ppm) to mask the potential influence of odor. Symptoms related to irritation and central nervous system effects were rated on 100-mm Visual Analogue Scales. Results: The ratings of eye irritation were slightly but significantly increased during exposure to acrolein in a dose-dependent manner (p < 0.001, Friedman test) with a median rating of 8 mm (corresponding to “hardly at all”) at the 0.1 ppm condition and with no influence from EA. No significant exposure-related effects were found for pulmonary function, or nasal swelling, nor for markers of inflammation and coagulation in blood (IL-6, C-reactive protein, serum amyloid A, fibrinogen, factor VIII, von Willebrand factor, and Clara cell protein) or induced sputum (cell count, differential cell count, IL-6 and IL-8). Blink frequency recorded by electromyography was increased during exposure to 0.1 ppm acrolein alone but not during any of the other five exposure conditions. Conclusion: Based on subjective ratings, the present study showed minor eye irritation by exposure to 0.1 ppm acrolein. PMID:26635308

  6. Metabolic shift in lung alveolar cell mitochondria following acrolein exposure.

    PubMed

    Agarwal, Amit R; Yin, Fei; Cadenas, Enrique

    2013-11-15

    Acrolein, an α,β unsaturated electrophile, is an environmental pollutant released in ambient air from diesel exhausts and cooking oils. This study examines the role of acrolein in altering mitochondrial function and metabolism in lung-specific cells. RLE-6TN, H441, and primary alveolar type II (pAT2) cells were exposed to acrolein for 4 h, and its effect on mitochondrial oxygen consumption rates was studied by XF Extracellular Flux analysis. Low-dose acrolein exposure decreased mitochondrial respiration in a dose-dependent manner because of alteration in the metabolism of glucose in all the three cell types. Acrolein inhibited glyceraldehyde-3-phosphate dehydrogenase (GAPDH) activity, leading to decreased substrate availability for mitochondrial respiration in RLE-6TN, H441, and pAT2 cells; the reduced GAPDH activity was compensated in pAT2 cells by an increase in the activity of glucose-6-phosphate dehydrogenase, the regulatory control of the pentose phosphate pathway. The decrease in pyruvate from glucose metabolism resulted in utilization of alternative sources to support mitochondrial energy production: palmitate-BSA complex increased mitochondrial respiration in RLE-6TN and pAT2 cells. The presence of palmitate in alveolar cells for surfactant biosynthesis may prove to be the alternative fuel source for mitochondrial respiration. Accordingly, a decrease in phosphatidylcholine levels and an increase in phospholipase A2 activity were found in the alveolar cells after acrolein exposure. These findings have implications for understanding the decrease in surfactant levels frequently observed in pathophysiological situations with altered lung function following exposure to environmental toxicants.

  7. Preliminary field trials of acrolein in the Sudan*

    PubMed Central

    Ferguson, Frederick F.; Dawood, Ismail K.; Blondeau, René

    1965-01-01

    Field trials of acrolein for the simultaneous control of aquatic weeds and snails were conducted in the Sudan. Phytotoxicity studies at 25 and 50 ppm showed minor or no damage to furrow-irrigated crops, but flood irrigation of vegetable seedlings at 15 ppm was toxic. Effective downstream carriage of acrolein was demonstrated for a distance of 1.6 km at a concentration of 25 ppm. Planorbid snails (Bulinus and Biomphalaria) were almost completely eliminated (98-99% kills). All submersed aquatic weeds were destroyed. PMID:14310912

  8. Aerobic and anaerobic growth of Paracoccus denitrificans on methanol.

    PubMed

    Bamforth, C W; Quayle, J R

    1978-10-01

    1. The dye-linked methanol dehydrogenase from Paracoccus denitrificans grown aerobically on methanol has been purified and its properties compared with similar enzymes from other bacteria. It was shown to be specific and to have high affinity for primary alcohols and formaldehyde as substrate, ammonia was the best activator and the enzyme could be linked to reduction of phenazine methosulphate. 2. Paracoccus denitrificans could be grown anaerobically on methanol, using nitrate or nitrite as electron acceptor. The methanol dehydrogenase synthesized under these conditions could not be differentiated from the aerobically-synthesized enzyme. 3. Activities of methanol dehydrogenase, formaldehyde dehydrogenase, formate dehydrogenase, nitrate reductase and nitrite reductase were measured under aerobic and anaerobic growth conditions. 4. Difference spectra of reduced and oxidized cytochromes in membrane and supernatant fractions of methanol-grown P. denitrificans were measured. 5. From the results of the spectral and enzymatic analyses it has been suggested that anaerobic growth on methanol/nitrate is made possible by reduction of nitrate to nitrite using electrons derived from the pyridine nucleotide-linked dehydrogenations of formaldehyde and formate, the nitrite so produced then functioning as electron acceptor for methanol dehydrogenase via cytochrome c and nitrite reductase. PMID:718372

  9. Oxidation of C1 compounds by particulate fractions from Methylococcus capsulatus: properties of methanol oxidase and methanol dehydrogenase.

    PubMed Central

    Wadzinski, A M; Ribbons, D W

    1975-01-01

    Methanol (and formaldehyde) oxidizing activities in crude extracts of Methylococcus capsulatus are associated mainly with particulate fractions sedimenting between 3,000 and 40,000 X g. Most of the phenazine methosulfate (PMS)-dependent methanol (and formaldehyde) dehydrogenase activity observed resides in the soluble fraction but represents only 40% of the total (PMS dependent plus independent) activity. Both PMS-dependent methanol dehydrogenase activity and PMS-independent methanol oxidase activity are found in particulate fractions, and the PMS-dependent dehydrogenase is easily solubilized by treatment with certain phospholipases or detergents. The properties of the PMS-dependent dehydrogenase activities in the soluble fraction and that solubilized from the particles suggested that they may be identical proteins. Their pH optima, temperature dependence, thermolabilities, and sensitivities to the presence of specific antisera were indistinguishable. Homogeneous preparations of the enzyme proteins obtained from the soluble fractions of extracts and the particulate fractions solubilized by detergents had similar: (i) electrophoretic mobilities in native and denatured states (subunit size in sodium dodecyl sulfate 62,000 daltons); (ii) molecular radii under native conditions, (iii) visible absorption spectra, lambdamax 350 nm, (iv) kinetic constants for methanol and formaldehyde; (v) substrate specificity; and (vi) immunological characteristics--antisera to each enzyme preparation showed precipitin lines of identity to either of the enzymes. It is suggested that the major site of methanol and formaldehyde oxidation in M. capsulatus occurs on the intracytoplasmic membranes in vivo and is coupled to oxygen reduction. Images PMID:238947

  10. Enzymatic conversion of carbon dioxide to methanol: Enhanced methanol production in silica sol-gel matrices

    SciTech Connect

    Obert, R.; Dave, B.C.

    1999-12-29

    Strategies for effective conversion of atmospheric CO{sub 2} to methanol offer promising new technologies not only for recycling of the greenhouse gas but also for an efficient production of fuel alternatives. Partial hydrogenation of carbon dioxide has been accomplished by means of heterogeneous catalysis, electrocatalysis, and photocatalysis. Oxide-based catalysts are predominantly used for industrial fixation of carbon dioxide. A unique approach in this direction involves the use of enzymes as catalysts for conversion of carbon dioxide to methanol. The use of enzymes is particularly appealing since it provides a facile low-temperature route for generation of methanol directly from gaseous carbon dioxide. The authors report an enzymatically coupled sequential reduction of carbon dioxide to methanol by using a series of reactions catalyzed by three different dehydrogenases. Overall, the process involves an initial reduction of CO{sub 2} to formate catalyzed by formate dehydrogenase (F{sub ate}DH), followed by reduction of formate to formaldehyde by formaldehyde dehydrogenase (F{sub ald}DH), and finally formaldehyde is reduced to methanol by alcohol dehydrogenase (ADH). In this process, reduced nicotinamide adenine dinucleotide (NADH) acts as a terminal electron donor for each dehydrogenase-catalyzed reduction.

  11. 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); ...

  12. Isomers of 3-(4-nitrophenyl)acrolein oxime

    SciTech Connect

    Leitis, L.Ya.; Liepin'sh, E.E.; Yansone, D.P.; Dreibante, I.I.; Shimanskaya, M.V.; Maslii, L.K.; Nikol'skaya, G.S.

    1986-06-10

    The Z and E isomers of 3-(4-nitrophenyl)acrolein oxime were obtained and characterized. The assignment was made on the basis of the geminal hetero constants /sup 2/J(/sup 15/N = C-/sup 1/H) and /sup 2/J(/sup 15/N = C-/sup 13/C).

  13. 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.

  14. The combined oxidation of methanol and ethanol on silver catalysts

    SciTech Connect

    Kurina, L.N.; Gryaznov, V.M.; Gul yanova, S.G.; Plakidkin, A.A.; Vedernikov, V.I.

    1985-10-01

    The authors study the oxidation of methanol, ethanol, and mixtures of these alcohols on industrial silver-pumice and silver membrane catalysts as well as the adsorption of these alcohols on silver. The oxidation of the alcohol mixture on the industrial silver-pumice catalyst gives higher yields of both formaldehyde and acetaldehyde than in the oxidation of the alcohols taken individually. It is also shown that an increase in the rates of formaldehyde formation in the combined oxidation of methanol and ethanol was observed on the silver membrane catalyst.

  15. 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. PMID:26969371

  16. Protein-bound acrolein: a novel marker of oxidative stress in Alzheimer's disease.

    PubMed

    Calingasan, N Y; Uchida, K; Gibson, G E

    1999-02-01

    Several lines of evidence support the role of oxidative stress, including increased lipid peroxidation, in the pathogenesis of Alzheimer's disease (AD). Lipid peroxidation generates various reactive aldehydes, such as 4-hydroxynonenal (HNE), which have been detected immunochemically in AD, particularly in neurofibrillary tangles, one of the major diagnostic lesions in AD brains. A recent study demonstrated that acrolein, the most reactive among the alpha,beta-unsaturated aldehyde products of lipid peroxidation, could be rapidly incorporated into proteins, generating a carbonyl derivative, a marker of oxidative stress to proteins. The current studies used an antibody raised against acrolein-modified keyhole limpet hemocyanin (KLH) to test whether acrolein modification of proteins occurs in AD. Double immunofluorescence revealed strong acrolein-KLH immunoreactivity in more than half of all paired helical filament (PHF)-1-labeled neurofibrillary tangles in AD cases. Acrolein-KLH immunoreactivity was also evident in a few neurons lacking PHF-1-positive neurofibrillary tangles. Light acrolein-KLH immunoreactivity occurred in dystrophic neurites surrounding the amyloid-beta core, which itself lacked acrolein-KLH staining. The pattern of acrolein-KLH immunostaining was similar to that of HNE. Control brains did not contain any acrolein-KLH-immunoreactive structures. The current results suggest that protein-bound acrolein is a powerful marker of oxidative damage to protein and support the hypothesis that lipid peroxidation and oxidative damage to protein may play a crucial role in the formation of neurofibrillary tangles and to neuronal death in AD.

  17. 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.

  18. The tobacco smoke component acrolein induces glucocorticoid resistant gene expression via inhibition of histone deacetylase.

    PubMed

    Randall, Matthew J; Haenen, Guido R M M; Bouwman, Freek G; van der Vliet, Albert; Bast, Aalt

    2016-01-01

    Chronic obstructive pulmonary disease (COPD) is the leading cause of cigarette smoke-related death worldwide. Acrolein, a crucial reactive electrophile found in cigarette smoke mimics many of the toxic effects of cigarette smoke-exposure in the lung. In macrophages, cigarette smoke is known to hinder histone deacetylases (HDACs), glucocorticoid-regulated enzymes that play an important role in the pathogenesis of glucocorticoid resistant inflammation, a common feature of COPD. Thus, we hypothesize that acrolein plays a role in COPD-associated glucocorticoid resistance. To examine the role of acrolein on glucocorticoid resistance, U937 monocytes, differentiated with PMA to macrophage-like cells were treated with acrolein for 0.5h followed by stimulation with hydrocortisone for 8h, or treated simultaneously with LPS and hydrocortisone for 8h without acrolein. GSH and nuclear HDAC activity were measured, or gene expression was analyzed by qPCR. Acrolein-mediated TNFα gene expression was not suppressed by hydrocortisone whereas LPS-induced TNFα expression was suppressed. Acrolein also significantly inhibited nuclear HDAC activity in macrophage-like cells. Incubation of recombinant HDAC2 with acrolein led to the formation of an HDAC2-acrolein adduct identified by mass spectrometry. Therefore, these results suggest that acrolein-induced inflammatory gene expression is resistant to suppression by the endogenous glucocorticoid, hydrocortisone.

  19. Acrolein generation stimulates hypercontraction in isolated human blood vessels

    SciTech Connect

    Conklin, D.J. . E-mail: dj.conklin@louisville.edu; Bhatnagar, A.; Cowley, H.R.; Johnson, G.H.; Trent, M.B.; Boor, P.J.

    2006-12-15

    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 H{sub 2}O{sub 2} exposure (1 {mu}M-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 {mu}M), (3) the vasoactive effects of two other SSAO amine substrates, benzylamine and methylamine, and (4) the contribution of extracellular Ca{sup 2+} to hypercontraction. Acrolein or allylamine but not H{sub 2}O{sub 2}, 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 Ca{sup 2+}-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.

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

    PubMed Central

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

    2012-01-01

    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. PMID:23026831

  1. 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.

  2. Determination of Urine 3-HPMA, a Stable Acrolein Metabolite in a Rat Model of Spinal Cord Injury

    PubMed Central

    Zheng, Lingxing; Park, Jonghyuck; Walls, Michael; Tully, Melissa; Jannasch, Amber; Cooper, Bruce

    2013-01-01

    Abstract Acrolein has been suggested to be involved in a variety of pathological conditions. The monitoring of acrolein is of significant importance in delineating the pathogenesis of various diseases. Aimed at overcoming the reactivity and volatility of acrolein, we describe a specific and stable metabolite of acrolein in urine, N-acetyl-S-3-hydroxypropylcysteine (3-HPMA), as a potential surrogate marker for acrolein quantification. Using the LC/MS/MS method, we demonstrated that 3-HPMA was significantly elevated in a dose-dependent manner when acrolein was injected into rats IP or directly into the spinal cord, but not when acrolein scavengers were co-incubated with acrolein solution. A nonlinear mathematic relationship is established between acrolein injected directly into the spinal cord and a correlated dose-dependent increase of 3-HPMA, suggesting the increase of 3-HPMA becomes less apparent as the level of injected acrolein increases. The elevation of 3-HPMA was further detected in the rat spinal cord injury, a pathological condition known to be associated with elevated endogenous acrolein. This finding was further validated by concomitant confirmation of increased acrolein-lysine adducts using established dot immunoblotting techniques. The noninvasive nature of measuring 3-HPMA concentrations in urine allows for long-term monitoring of acrolein in the same animal and ultimately in human clinical studies. Due to wide spread involvement of acrolein in human health, the benefits of this study have the potential to enhance human health significantly. PMID:23697633

  3. Determination of urine 3-HPMA, a stable acrolein metabolite in a rat model of spinal cord injury.

    PubMed

    Zheng, Lingxing; Park, Jonghyuck; Walls, Michael; Tully, Melissa; Jannasch, Amber; Cooper, Bruce; Shi, Riyi

    2013-08-01

    Acrolein has been suggested to be involved in a variety of pathological conditions. The monitoring of acrolein is of significant importance in delineating the pathogenesis of various diseases. Aimed at overcoming the reactivity and volatility of acrolein, we describe a specific and stable metabolite of acrolein in urine, N-acetyl-S-3-hydroxypropylcysteine (3-HPMA), as a potential surrogate marker for acrolein quantification. Using the LC/MS/MS method, we demonstrated that 3-HPMA was significantly elevated in a dose-dependent manner when acrolein was injected into rats IP or directly into the spinal cord, but not when acrolein scavengers were co-incubated with acrolein solution. A nonlinear mathematic relationship is established between acrolein injected directly into the spinal cord and a correlated dose-dependent increase of 3-HPMA, suggesting the increase of 3-HPMA becomes less apparent as the level of injected acrolein increases. The elevation of 3-HPMA was further detected in the rat spinal cord injury, a pathological condition known to be associated with elevated endogenous acrolein. This finding was further validated by concomitant confirmation of increased acrolein-lysine adducts using established dot immunoblotting techniques. The noninvasive nature of measuring 3-HPMA concentrations in urine allows for long-term monitoring of acrolein in the same animal and ultimately in human clinical studies. Due to wide spread involvement of acrolein in human health, the benefits of this study have the potential to enhance human health significantly.

  4. Melamine-formaldehyde aerogels

    SciTech Connect

    Alviso, C.T.; Pekala, R.W.

    1991-04-01

    The ability to tailor the structure and properties of aerogels at the nanometer scale opens up exciting possibilities for these unique, low density materials. Traditional inorganic aerogels have been formed from the hydrolysis and condensation of metal alkoxides (e.g. tetramethoxy silane). Previously, we reported the synthesis of organic aerogels based upon the aqueous, polycondensation of resorcinol with formaldehyde. Although these aerogels exhibit minimal light scattering, their dark red color limits their use in certain optical applications. In this paper, we discuss the synthesis and characterization of melamine-formaldehyde aerogels -- a new type of organic aerogel that is both colorless and transparent. 16 refs., 3 figs., 1 tab.

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

    SciTech Connect

    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. -- Highlights: ► Human primary hepatocytes and cultured cell lines are used. ► Multiple cell death signaling pathways are activated by acrolein. ► Novel finding of

  6. Methanol: a chemical Trojan horse as the root of the inscrutable U.

    PubMed

    Monte, Woodrow C

    2010-03-01

    Until 200 years ago, methanol was an extremely rare component of the human diet and is still rarely consumed in contemporary hunter and gatherer cultures. With the invention of canning in the 1800s, canned and bottled fruits and vegetables, whose methanol content greatly exceeds that of their fresh counterparts, became far more prevalent. The recent dietary introduction of aspartame, an artificial sweetener 11% methanol by weight, has also greatly increased methanol consumption. Moreover, methanol is a major component of cigarette smoke, known to be a causative agent of many diseases of civilization (DOC). Conversion to formaldehyde in organs other than the liver is the principal means by which methanol may cause disease. The known sites of class I alcohol dehydrogenase (ADH I), the only human enzyme capable of metabolizing methanol to formaldehyde, correspond to the sites of origin for many DOC. Variability in sensitivity to exogenous methanol consumption may be accounted for in part by the presence of aldehyde dehydrogenase sufficient to reduce the toxic effect of formaldehyde production in tissue through its conversion to the much less toxic formic acid. The consumption of small amounts of ethanol, which acts as a competitive inhibitor of methanol's conversion to formaldehyde by ADH I, may afford some individuals protection from DOC.

  7. Enzymatic synthesis of C-11 formaldehyde: concise communication

    SciTech Connect

    Slegers, G.; Lambrecht, R.H.D.; Vandewalle, T.; Meulewaeter, L.; Vandecasteele, C.

    1984-03-01

    An enzymatic synthesis of C-11 formaldehyde from C-11 methanol is presented, with immobilized alcohol oxidase and catalase: a rapid, simple procedure, with a high and reproducible yield. Carbon-11 methanol is oxidized to C-11 formaldehyde by passage over a column on which the enzymes alcohol oxidase and catalase are immobilized. The catalase increases reaction velocity by recycling the oxygen, and prevents destruction of the alcohol oxidase by eliminating the excess of hydrogen peroxide. The yield of the enzyme-catalyzed oxidation was 80-95%. A specific activity of 400-450 mCi/..mu..mole was obtained at EOB + 20 min. Various immobilization techniques and the optimal reaction conditions of the immobilized enzymes are investigated.

  8. Inhibition by acrolein of light-induced stomatal opening through inhibition of inward-rectifying potassium channels in Arabidopsis thaliana.

    PubMed

    Islam, Md Moshiul; Ye, Wenxiu; Matsushima, Daiki; Khokon, Md Atiqur Rahman; Munemasa, Shintaro; Nakamura, Yoshimasa; Murata, Yoshiyuki

    2015-01-01

    Acrolein is a reactive α,β-unsaturated aldehyde derived from lipid peroxides, which are produced in plants under a variety of stress. We investigated effects of acrolein on light-induced stomatal opening using Arabidopsis thaliana. Acrolein inhibited light-induced stomatal opening in a dose-dependent manner. Acrolein at 100 μM inhibited plasma membrane inward-rectifying potassium (Kin) channels in guard cells. Acrolein at 100 μM inhibited Kin channel KAT1 expressed in a heterologous system using Xenopus leaves oocytes. These results suggest that acrolein inhibits light-induced stomatal opening through inhibition of Kin channels in guard cells.

  9. Acrolein detection: potential theranostic utility in multiple sclerosis and spinal cord injury

    PubMed Central

    Tully, Melissa; Zheng, Lingxing; Shi, Riyi

    2015-01-01

    Oxidative stress has been implicated as a major pathological process underlying CNS disease and trauma. More specifically, acrolein, an unsaturated aldehyde, produced by way of lipid peroxidation, has been shown to play a crucial role in initiating and perpetuating detrimental effects associated with multiple sclerosis and spinal cord injury. In light of these findings, quantification of acrolein levels both systemically and locally could allow for the use of acrolein as a biomarker to aid in diagnosis and guide treatment regimens. The three main approaches currently available are acrolein derivatization followed byLC/GC–MS, application of an acrolein antibody and subsequent immunoblotting, and the 3-hydroxypropylmercapturic acid-based method. Of these three strategies, the 3-hydroxypropylmercapturic acid-based method is the least invasive allowing for rapid translation of acrolein detection into a clinical setting. PMID:24831349

  10. Acrolein detection: potential theranostic utility in multiple sclerosis and spinal cord injury.

    PubMed

    Tully, Melissa; Zheng, Lingxing; Shi, Riyi

    2014-06-01

    Oxidative stress has been implicated as a major pathological process underlying CNS disease and trauma. More specifically, acrolein, an unsaturated aldehyde, produced by way of lipid peroxidation, has been shown to play a crucial role in initiating and perpetuating detrimental effects associated with multiple sclerosis and spinal cord injury. In light of these findings, quantification of acrolein levels both systemically and locally could allow for the use of acrolein as a biomarker to aid in diagnosis and guide treatment regimens. The three main approaches currently available are acrolein derivatization followed by LC/GC-MS, application of an acrolein antibody and subsequent immunoblotting, and the 3-hydroxypropylmercapturic acid-based method. Of these three strategies, the 3-hydroxypropylmercapturic acid-based method is the least invasive allowing for rapid translation of acrolein detection into a clinical setting.

  11. Lipid peroxidation product acrolein as a predictive biomarker of prostate carcinoma relapse after radical surgery.

    PubMed

    Custovic, Zajim; Zarkovic, Kamelija; Cindric, Marina; Cipak, Ana; Jurkovic, Ilija; Sonicki, Zdenko; Uchida, Koji; Zarkovic, Neven

    2010-05-01

    Cancer recurrence after radical surgery might happen even in the case of patients with localized prostate carcinoma treated by radical prostatectomy. Therefore, identifying predictive markers of tumour recurrence is very important, so this study evaluated the presence of lipid peroxidation product acrolein in primary prostate carcinomas, assuming that acrolein could be involved in prostate carcinogenesis as was recently shown for colon cancer. Samples obtained by radical prostatectomy of 70 patients were analysed, out of which 27 patients suffered afterwards from tumour recurrence, while 43 patients were disease free. Immunohistochemistry using genuine monoclonal antibodies against acrolein-protein adducts revealed the association of acrolein with progression of carcinoma. The logistic regression combining clinical parameters together with the biochemical markers of disease and acrolein immunohistochemistry has shown that the relapse might be predicted with 90% accuracy if tumour-positive surgical margins, stage of disease and the intensity of acrolein presence in tumour stroma were taken together.

  12. Formaldehyde from GOME-2

    NASA Astrophysics Data System (ADS)

    Comyn-Platt, Edward; Hewson, Will; Bösch, Hartmut; Barkley, Mike

    2014-05-01

    Isoprene is the most abundant non-methane biogenic volatile organic compound (BVOC) emitted into the atmosphere with emissions roughly equal to global methane emissions from all sources. Isoprene strongly influences the oxidation capacity in the troposphere hence influences levels of methane and tropospheric ozone, and is also a precursor to secondary organic aerosol. Isoprene, therefore, plays a significant role in radiative forcing and determining Earth's climate trends. However, the exact mechanisms of isoprene emission from vegetation are poorly understood and current land-surface models often use different parameterisation and meteorological fields to drive such schemes. Furthermore, isoprene emissions measurements are rare and are difficult to extrapolate to regional and continental scales thus resulting in large uncertainties in the total global emissions. Formaldehyde (HCHO) is formed as an intermediate product during the isoprene oxidation process and can be used as a proxy for isoprene emission. Global satellite observations of formaldehyde are now available from a number of satellite sensors which offer a unique ability to study isoprene emissions over large regions. Here, we use formaldehyde observations from the Global Ozone Monitoring Experiment 2 (GOME-2) instrument retrieved with the University of Leicester retrieval (Hewson et al. 2013) to: 1) test state-of-the-art model calculations using the GEOS-CHEM global transport model; 2) investigate the key drivers for regional year-to-year anomalies in formaldehyde (or isoprene) emissions and 3) assess the ability of current land surface models (MEGAN, JULES) to reproduce the observed anomalies and their dependence on climate variations.

  13. ORAL EXPOSURE TO ACROLEIN EXACERBATES ATHEROSCLEROSIS IN APO E-NULL MICE

    PubMed Central

    Srivastava, Sanjay; Sithu, Srinivas D.; Vladykovskaya, Elena; Haberzettl, Petra; Hoetker, David J.; Siddiqui, Maqsood A.; Conklin, Daniel J.; D'Souza, Stanley E.; Bhatnagar, Aruni

    2011-01-01

    Background Acrolein is a dietary aldehyde that is present in high concentrations in alcoholic beverages and foods including cheese, donuts and coffee. It is also abundant in tobacco smoke, automobile exhaust and industrial waste and is generated in vivo during inflammation and oxidative stress. Objectives The goal of this study was to examine the effects of dietary acrolein on atherosclerosis. Methods Eight-week old male apoE-null mice were gavage-fed acrolein (2.5 mg/kg/day) for 8 weeks. Atherosclerotic lesion formation and composition and plasma lipids and platelet factor 4 (PF4) levels were measured. Effects of acrolein and PF4 on endothelial cell function was measured in vitro. Results Acrolein feeding increased the concentration of cholesterol in the plasma. NMR analysis of the lipoproteins showed that acrolein feeding increased the abundance of small and medium VLDL particles. Acrolein feeding also increased atherosclerotic lesion formation in the aortic valve and the aortic arch. Immunohistochemical analysis showed increased macrophage accumulation in the lesions of acrolein-fed mice. Plasma PF4 levels and accumulation of PF4 in atherosclerotic lesions was increased in the acrolein-fed mice. Incubation of endothelial cells with the plasma of acrolein-fed mice augmented transmigration of monocytic cells, which was abolished by anti-PF4 antibody treatment. Conclusions Dietary exposure to acrolein exacerbates atherosclerosis in apoE-null mice. Consumption of foods and beverages rich in unsaturated aldehydes such as acrolein may be a contributing factor to the progression of atherosclerotic lesions. PMID:21371710

  14. Acrolein induces vasodilatation of rodent mesenteric bed via an EDHF-dependent mechanism

    SciTech Connect

    Awe, S.O.; Adeagbo, A.S.O.; D'Souza, S.E.; Bhatnagar, A.; Conklin, D.J. . E-mail: dj.conklin@louisville.edu

    2006-12-15

    Acrolein is generated endogenously during lipid peroxidation and inflammation and is an environmental pollutant. Protein adducts of acrolein are detected in atherosclerotic plaques and neurons of patients with Alzheimer's disease. To understand vascular effects of acrolein exposure, we studied acrolein vasoreactivity in perfused rodent mesenteric bed. Acrolein induced endothelium-dependent vasodilatation that was more robust and more sensitive than dilation induced by 4-hydroxy-trans-2-nonenal, trans-2-hexenal, or propionaldehyde. Acrolein-induced vasodilatation was mediated by K{sup +}-sensitive components, e.g., it was abolished in 0 [K{sup +}]{sub o} buffer or in 3 mM tetrabutylammonium, inhibited 75% in 50 {mu}M ouabain, and inhibited 64% in 20 mM K{sup +} buffer. Moreover, combined treatment with the Ca{sup 2+}-activated K{sup +} channel inhibitors 1-[(2-chlorophenyl)diphenylmethyl]-1H-pyrazole (TRAM-34, 100 nM) and apamin (5 {mu}M) significantly reduced vasodilatation without altering sensitivity to acrolein. However, acrolein-induced % dilation was unaffected by L-NAME or indomethacin pretreatment indicating mechanistic independence of NO and prostaglandins. Moreover, acrolein induced vasodilatation in cirazoline-precontracted mesenteric bed of eNOS-null mice confirming eNOS independence. Pretreatment with 6-(2-propargyloxyphenyl) hexanoic acid (PPOH 50 {mu}M), an epoxygenase inhibitor, or the superoxide dismutase mimetic Tempol (100 {mu}M) significantly attenuated acrolein-induced vasodilatation. Collectively, these data indicate that acrolein stimulates mesenteric bed vasodilatation due to endothelium-derived signal(s) that is K{sup +}-, ouabain-, PPOH-, and Tempol-sensitive, and thus, a likely endothelium-derived hyperpolarizing factor (EDHF). These data indicate that low level acrolein exposure associated with vascular oxidative stress or inflammation stimulates vasodilatation via EDHF release in medium-sized arteries - a novel function.

  15. The kinetics behavior of the reduction of formaldehyde catalyzed by Alcohol Dehydrogenase (ADH) and partial uncompetitive substrate inhibition by NADH.

    PubMed

    Wen, Nuan; Liu, Wenfang; Hou, Yanhui; Zhao, Zhiping

    2013-05-01

    Alcohol dehydrogenase (ADH) catalyzes the final step in the biosynthesis of methanol from CO2. Here, we report the steady-state kinetics for ADH, using a homogeneous enzyme preparation with formaldehyde as the substrate and nicotinamide adenine dinucleotide (NADH) as the cofactor. When changing NADH concentrations with the fixed concentrations of HCHO (more or less than NADH), kinetic studies revealed a particular zigzag phenomenon for the first time. Increasing formaldehyde concentration can weaken substrate inhibition and improve catalytic efficiency. The kinetic mechanism of ADH was analyzed using the secondary fitting method. The double reciprocal plots (1/v∼1/[HCHO] and 1/[NADH]) strongly demonstrated that the substrate inhibition by NADH was uncompetitive versus formaldehyde and partial. In the direction of formaldehyde reduction, ADH has an ordered kinetic mechanism with formaldehyde adding to enzyme first and product methanol released last. The second reactant NADH can combine with the enzyme-methanol complex and then methanol dissociates from it at a slower rate than from enzyme-methanol. The reaction velocity depends on the relative rates of the alternative pathways. The addition of NADH also accelerates the releasing of methanol. As a result, substrate inhibition and activation occurred intermittently, and the zigzag double reciprocal plot (1/v∼1/[NADH]) was obtained.

  16. Coadsorbed species explain the mechanism of methanol temperature-desorption on CeO2(111)

    DOE PAGES

    Sutton, Jonathan E.; Steven H. Overbury; Beste, Ariana

    2016-03-24

    Here, we have used density functional theory calculations to investigate the temperature-programmed desorption (TPD) of methanol from CeO2(111). For the first time, low-temperature water formation and high-temperature methanol desorption are explained by our calculations. High coverages of methanol, which correspond to experimental conditions, are required to properly describe these features of the TPD spectrum. We identify a mechanism for the low-temperature formation of water involving the dissociation of two methanol molecules on the same surface O atom and filling of the resulting surface vacancy with one of the methoxy products. After water desorption, methoxy groups are stabilized on the surfacemore » and react at higher temperatures to form methanol and formaldehyde by a disproportionation mechanism. Alternatively, the stabilized methoxy groups undergo sequential C–H scission reactions to produce formaldehyde. Calculated energy requirements and methanol/formaldehyde selectivity agree with the experimental data.« less

  17. Unilateral microinjection of acrolein into thoracic spinal cord produces acute and chronic injury and functional deficits.

    PubMed

    Gianaris, Alexander; Liu, Nai-Kui; Wang, Xiao-Fei; Oakes, Eddie; Brenia, John; Gianaris, Thomas; Ruan, Yiwen; Deng, Ling-Xiao; Goetz, Maria; Vega-Alvarez, Sasha; Lu, Qing-Bo; Shi, Riyi; Xu, Xiao-Ming

    2016-06-21

    Although lipid peroxidation has long been associated with spinal cord injury (SCI), the specific role of lipid peroxidation-derived byproducts such as acrolein in mediating damage remains to be fully understood. Acrolein, an α-β unsaturated aldehyde, is highly reactive with proteins, DNA, and phospholipids and is considered as a second toxic messenger that disseminates and augments initial free radical events. Previously, we showed that acrolein increased following traumatic SCI and injection of acrolein induced tissue damage. Here, we demonstrate that microinjection of acrolein into the thoracic spinal cord of adult rats resulted in dose-dependent tissue damage and functional deficits. At 24h (acute) after the microinjection, tissue damage, motoneuron loss, and spinal cord swelling were observed on sections stained with Cresyl Violet. Luxol fast blue staining further showed that acrolein injection resulted in dose-dependent demyelination. At 8weeks (chronic) after the microinjection, cord shrinkage, astrocyte activation, and macrophage infiltration were observed along with tissue damage, neuron loss, and demyelination. These pathological changes resulted in behavioral impairments as measured by both the Basso, Beattie, and Bresnahan (BBB) locomotor rating scale and grid walking analysis. Electron microscopy further demonstrated that acrolein induced axonal degeneration, demyelination, and macrophage infiltration. These results, combined with our previous reports, strongly suggest that acrolein may play a critical causal role in the pathogenesis of SCI and that targeting acrolein could be an attractive strategy for repair after SCI. PMID:27058147

  18. The effects of acetaldehyde and acrolein on muscle catabolism in C2 myotubes.

    PubMed

    Rom, Oren; Kaisari, Sharon; Aizenbud, Dror; Reznick, Abraham Z

    2013-12-01

    The toxic aldehydes acetaldehyde and acrolein were previously suggested to damage skeletal muscle. Several conditions in which exposure to acetaldehyde and acrolein is increased were associated with muscle wasting and dysfunction. These include alcoholic myopathy, renal failure, oxidative stress, and inflammation. A main exogenous source of both acetaldehyde and acrolein is cigarette smoking, which was previously associated with increased muscle catabolism. Recently, we have shown that exposure of skeletal myotubes to cigarette smoke stimulated muscle catabolism via increased oxidative stress, activation of p38 MAPK, and upregulation of muscle-specific E3 ubiquitin ligases. In this study, we aimed to investigate the effects of acetaldehyde and acrolein on catabolism of skeletal muscle. Skeletal myotubes differentiated from the C2 myoblast cell line were exposed to acetaldehyde or acrolein and their effects on signaling pathways related to muscle catabolism were studied. Exposure of myotubes to acetaldehyde did not promote muscle catabolism. However, exposure to acrolein caused increased generation of free radicals, activation of p38 MAPK, upregulation of the muscle-specific E3 ligases atrogin-1 and MuRF1, degradation of myosin heavy chain, and atrophy of myotubes. Inhibition of p38 MAPK by SB203580 abolished acrolein-induced muscle catabolism. Our findings demonstrate that acrolein but not acetaldehyde activates a signaling cascade resulting in muscle catabolism in skeletal myotubes. Although within the limitations of an in vitro study, these findings indicate that acrolein may promote muscle wasting in conditions of increased exposure to this aldehyde.

  19. Neuroprotective role of hydralazine in rat spinal cord injury-attenuation of acrolein-mediated damage.

    PubMed

    Park, Jonghyuck; Zheng, Lingxing; Marquis, Andrew; Walls, Michael; Duerstock, Brad; Pond, Amber; Vega-Alvarez, Sasha; Wang, He; Ouyang, Zheng; Shi, Riyi

    2014-04-01

    Acrolein, an α,β-unsaturated aldehyde and a reactive product of lipid peroxidation, has been suggested as a key factor in neural post-traumatic secondary injury in spinal cord injury (SCI), mainly based on in vitro and ex vivo evidence. Here, we demonstrate an increase of acrolein up to 300%; the elevation lasted at least 2 weeks in a rat SCI model. More importantly, hydralazine, a known acrolein scavenger can provide neuroprotection when applied systemically. Besides effectively reducing acrolein, hydralazine treatment also resulted in significant amelioration of tissue damage, motor deficits, and neuropathic pain. This effect was further supported by demonstrating the ability of hydralazine to reach spinal cord tissue at a therapeutic level following intraperitoneal application. This suggests that hydralazine is an effective neuroprotective agent not only in vitro, but in a live animal model of SCI as well. Finally, the role of acrolein in SCI was further validated by the fact that acrolein injection into the spinal cord caused significant SCI-like tissue damage and motor deficits. Taken together, available evidence strongly suggests a critical causal role of acrolein in the pathogenesis of spinal cord trauma. Since acrolein has been linked to a variety of illness and conditions, we believe that acrolein-scavenging measures have the potential to be expanded significantly ensuring a broad impact on human health.

  20. Acrolein induced both pulmonary inflammation and the death of lung epithelial cells.

    PubMed

    Sun, Yang; Ito, Sachiko; Nishio, Naomi; Tanaka, Yuriko; Chen, Nana; Isobe, Ken-Ichi

    2014-09-01

    Acrolein, a compound found in cigarette smoke, is a major risk factor for respiratory diseases. Previous research determined that both acrolein and cigarette smoke produced reactive oxygen species (ROS). As many types of pulmonary injuries are associated with inflammation, this study sought to ascertain the extent to which exposure to acrolein advanced inflammatory state in the lungs. Our results showed that intranasal exposure of mice to acrolein increased CD11c(+)F4/80(high) macrophages in the lungs and increased ROS formation via induction of NF-κB signaling. Treatment with acrolein activated macrophages and led to their increased production of ROS and expression of several key pro-inflammatory cytokines. In in vitro studies, acrolein treatment of bone marrow-derived GM-CSF-dependent immature macrophages (GM-IMs), activated the cells and led to their increased production of ROS and expression of several key pro-inflammatory cytokines. Acrolein treatment of macrophages induced apoptosis of lung epithelial cells. Inclusion of an inhibitor of ROS formation markedly decreased acrolein-mediated macrophage activation and reduced the extent of epithelial cell death. These results indicate that acrolein can cause lung damage, in great part by mediating the increased release of pro-inflammatory cytokines/factors by macrophages.

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

    SciTech Connect

    Kim, Chae E.; Lee, Seung J.; Seo, Kyo W.; Park, Hye M.; Yun, Jung W.; Bae, Jin U.; Bae, Sun S.; Kim, Chi D.

    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 among 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.

  2. Hydralazine inhibits compression and acrolein-mediated injuries in ex vivo spinal cord.

    PubMed

    Hamann, Kristin; Nehrt, Genevieve; Ouyang, Hui; Duerstock, Brad; Shi, Riyi

    2008-02-01

    We have previously shown that acrolein, a lipid peroxidation byproduct, is significantly increased following spinal cord injury in vivo, and that exposure to neuronal cells results in oxidative stress, mitochondrial dysfunction, increased membrane permeability, impaired axonal conductivity, and eventually cell death. Acrolein thus may be a key player in the pathogenesis of spinal cord injury, where lipid peroxidation is known to be involved. The current study demonstrates that the acrolein scavenger hydralazine protects against not only acrolein-mediated injury, but also compression in guinea pig spinal cord ex vivo. Specifically, hydralazine (500 mumol/L to 1 mmol/L) can significantly alleviate acrolein (100-500 mumol/L)-induced superoxide production, glutathione depletion, mitochondrial dysfunction, loss of membrane integrity, and reduced compound action potential conduction. Additionally, 500 mumol/L hydralazine significantly attenuated compression-mediated membrane disruptions at 2 and 3 h following injury. This was consistent with our findings that acrolein-lys adducts were increased following compression injury ex vivo, an effect that was prevented by hydralazine treatment. These findings provide further evidence for the role of acrolein in spinal cord injury, and suggest that acrolein-scavenging drugs such as hydralazine may represent a novel therapy to effectively reduce oxidative stress in disorders such as spinal cord injury and neurodegenerative diseases, where oxidative stress is known to play a role.

  3. Field trials in Egypt with acrolein herbicide-molluscicide*

    PubMed Central

    Unrau, G. O.; Farooq, M.; Dawood, Ismail K.; Miguel, Luis C.; Dazo, B. C.

    1965-01-01

    Acrolein is a dual-purpose chemical effective against both submersed weeds and snails, and it may therefore be of significance in bilharziasis control. During trials in the Egypt-49-project area in 1962, it was effective in clearing heavy mats of the major submersed aquatic weed Potamogeton crispus from irrigation canals. The resurgence of snails to pretreatment levels was delayed by 8-12 months, and submersed weeds did not reappear until 8 months after treatment. In phytotoxicity tests on local crops, it was found that the concentration of acrolein required for destroying submersed weeds (20-25 ppm) had no adverse effect on the crops. The field tests showed that it is important to have complete control of the water during the period of application. PMID:14310913

  4. Selective oxidation of ethane to acetaldehyde and acrolein over silica-supported vanadium catalysts using oxygen as oxidant

    SciTech Connect

    Zhao, Zhen; Yamada, Yusuke; Teng, Yonghong; Ueda, Atsushi; Nakagawa, Kiyoharu; Kobayashi, Tetsuhiko

    2000-03-10

    The oxidation of ethane by oxygen was studied over silica catalysts supporting different amounts of vanadium with and without cesium. Three different catalytic properties of the product selectivity were observed, aldehyde formation, oxidative dehydrogenation (ODH), and combustion, depending upon the vanadium loading amount and the presence or the absence of cesium. A very low loading of vanadium (V:Si = 0.02--0.1 at.%) and the addition of Cs (Cs:Si = 1 at.%) on silica were found to be important for the formation of aldehyde. Not only acetaldehyde but also acrolein were observed in the aldehyde formation from ethane. On the other hand, catalysts with medium and high vanadium loadings (V:Si = 0.5--20 at.%) gave a dehydrogenated product, ethene, when Cs was not added to the catalysts. The addition of cesium to the catalysts with medium and high vanadium loadings changed the catalytic property from ODH to combustion. The different types of vanadyl species were identified by UV-visible and IR measurements in samples with different vanadium loadings. It was estimated that isolated vanadyl species with tetrahedral coordination, which were found mainly on the catalysts with vanadium loading lower than 0.5 at.%, became the active site for the aldehyde formation through the interaction with Cs. As a plausible reaction path giving acrolein from ethane, cesium-catalyzed cross-condensation between acetaldehyde and formaldehyde, formed in the reaction, was proposed. Polymeric vanadyl species with octahedral coordination were detected in the samples with medium (0.5--5.0 at.%) and high (10 and 20 at.%) vanadium loadings, respectively. Both species show the ODH catalytic property without cesium, but they bring about a deep oxidation of ethane if cesium is added to the catalysts.

  5. Critical review of the literature on acrolein toxicity

    SciTech Connect

    Beauchamp, R.O. Jr.; Andjelkovich, D.A.; Kligerman, A.D.; Morgan, K.T.; Heck, H.D.

    1985-01-01

    A detailed literature review with 520 references of human and animal toxicity studies of acrolein is presented, and information gaps identified that call for further investigation. Specific recommendations are suggested for additional short-/long-term studies, including chemical disposition and cytogenetic investigations. Two bibliographies are provided indicating the scope of the review: (1) literature actually cited and (2) literature examined but not included. 520 references.

  6. Formation of Hydroxymethyl DNA Adducts in Rats Orally Exposed to Stable Isotope Labeled Methanol

    PubMed Central

    Lu, Kun; Gul, Husamettin; Upton, Patricia B.; Moeller, Benjamin C.; Swenberg, James A.

    2012-01-01

    Methanol is a large volume industrial chemical and widely used solvent and fuel additive. Methanol’s well known toxicity and use in a wide spectrum of applications has raised long-standing environmental issues over its safety, including its carcinogenicity. Methanol has not been listed as a carcinogen by any regulatory agency; however, there are debates about its carcinogenic potential. Formaldehyde, a metabolite of methanol, has been proposed to be responsible for the carcinogenesis of methanol. Formaldehyde is a known carcinogen and actively targets DNA and protein, causing diverse DNA and protein damage. However, formaldehyde-induced DNA adducts arising from the metabolism of methanol have not been reported previously, largely due to the absence of suitable DNA biomarkers and the inability to differentiate what was due to methanol compared with the substantial background of endogenous formaldehyde. Recently, we developed a unique approach combining highly sensitive liquid chromatography-mass spectrometry methods and exposure to stable isotope labeled chemicals to simultaneously quantify formaldehyde-specific endogenous and exogenous DNA adducts. In this study, rats were exposed daily to 500 or 2000 mg/kg [13CD4]-methanol by gavage for 5 days. Our data demonstrate that labeled formaldehyde arising from [13CD4]-methanol induced hydroxymethyl DNA adducts in multiple tissues in a dose-dependent manner. The results also demonstrated that the number of exogenous DNA adducts was lower than the number of endogenous hydroxymethyl DNA adducts in all tissues of rats administered 500 mg/kg per day for 5 days, a lethal dose to humans, even after incorporating an average factor of 4 for reduced metabolism due to isotope effects of deuterium-labeled methanol into account. PMID:22157354

  7. OF MICE, MEN, MONKEYS AND METABOLISM: AN UPDATE ON THE DEVELOPMENTAL TOXICITY OF METHANOL

    EPA Science Inventory

    With a world production ca. 30 million tons per year, methanol is a solvent, is used to produce formaldehyde, MTBE, and acetic acid, is a component of aspartame, and has been proposed as an alternate vehicle fuel. Methanol occurs naturally in plants and animals. It is sequentiall...

  8. 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...

  9. 40 CFR 63.2240 - What are the compliance options and operating requirements and how must I meet them?

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... the definition of biofilter in § 63.2292, you must use 40 CFR part 63, appendix C, Determination of... include acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde from your...

  10. 40 CFR 63.2240 - What are the compliance options and operating requirements and how must I meet them?

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... the definition of biofilter in § 63.2292, you must use 40 CFR part 63, appendix C, Determination of... include acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde from your...

  11. 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

    ... the definition of biofilter in § 63.2292, you must use 40 CFR part 63, appendix C, Determination of... include acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde from your...

  12. 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

    ... the definition of biofilter in § 63.2292, you must use 40 CFR part 63, appendix C, Determination of... include acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde from your...

  13. 40 CFR 63.2240 - What are the compliance options and operating requirements and how must I meet them?

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... the definition of biofilter in § 63.2292, you must use 40 CFR part 63, appendix C, Determination of... include acetaldehyde, acrolein, formaldehyde, methanol, phenol, and propionaldehyde from your...

  14. Engineering Escherichia coli for methanol conversion.

    PubMed

    Müller, Jonas E N; Meyer, Fabian; Litsanov, Boris; Kiefer, Patrick; Potthoff, Eva; Heux, Stéphanie; Quax, Wim J; Wendisch, Volker F; Brautaset, Trygve; Portais, Jean-Charles; Vorholt, Julia A

    2015-03-01

    Methylotrophic bacteria utilize methanol and other reduced one-carbon compounds as their sole source of carbon and energy. For this purpose, these bacteria evolved a number of specialized enzymes and pathways. Here, we used a synthetic biology approach to select and introduce a set of "methylotrophy genes" into Escherichia coli based on in silico considerations and flux balance analysis to enable methanol dissimilation and assimilation. We determined that the most promising approach allowing the utilization of methanol was the implementation of NAD-dependent methanol dehydrogenase and the establishment of the ribulose monophosphate cycle by expressing the genes for hexulose-6-phosphate synthase (Hps) and 6-phospho-3-hexuloisomerase (Phi). To test for the best-performing enzymes in the heterologous host, a number of enzyme candidates from different donor organisms were selected and systematically analyzed for their in vitro and in vivo activities in E. coli. Among these, Mdh2, Hps and Phi originating from Bacillus methanolicus were found to be the most effective. Labeling experiments using (13)C methanol with E. coli producing these enzymes showed up to 40% incorporation of methanol into central metabolites. The presence of the endogenous glutathione-dependent formaldehyde oxidation pathway of E. coli did not adversely affect the methanol conversion rate. Taken together, the results of this study represent a major advancement towards establishing synthetic methylotrophs by gene transfer.

  15. Molecular regulations induced by acrolein in neuroblastoma SK-N-SH cells: relevance to Alzheimer's disease.

    PubMed

    Dang, Thanh Nam; Arseneault, Madeleine; Zarkovic, Neven; Waeg, Georg; Ramassamy, Charles

    2010-01-01

    Acrolein is the most reactive aldehyde among the by-products of lipid peroxidation. Growing evidence indicates that acrolein may play an important role in the pathogenesis of Alzheimer's disease (AD). In AD, levels of acrolein are significantly higher in hippocampus and temporal cortex regions of the brain. However, little is known about its toxicity in neuronal cells. Using the neuroblastoma cell line SK-N-SH, our results show that acrolein is toxic from 10 μM, but its toxicity does not induce the activation of caspase-3 and DNA fragmentation. Protein carbonylation and 4-hydroxynonenal levels were increased after 0.5 hr and 1 hr of treatment, respectively. Furthermore acrolein induced a biphasic effect on glutathione levels with a rapid depletion followed by a progressive increase. We have further investigated the regulation of different redox signaling pathways. A treatment with 10 μM of acrolein for 30 min activated NFκB while this activation was suppressed after a 24 hrs of treatment. In contrast, Nrf2 was activated only after 24 hrs of acrolein exposure. Consequently, the expression of heme oxygenase-1 and γ-glutamyl-cysteine-synthase were elevated after 24 hrs of acrolein treatment. Sirt-1 was also upregulated after 24 hrs of acrolein treatment. The p66Shc and ERK1/2 proteins are known to be involved in oxidative stress. Acrolein, at 10 μM, induced the phosphorylation of p66Shc and ERK1/2 only after a short period of treatment. Collectively, these data strengthen the contribution of acrolein in the induction of oxidative stress as observed in mild cognitive impairment and in AD brain.

  16. Aldose reductase regulates acrolein-induced cytotoxicity in human small airway epithelial cells.

    PubMed

    Yadav, Umesh C S; Ramana, K V; Srivastava, Satish K

    2013-12-01

    Aldose reductase (AR), a glucose-metabolizing enzyme, reduces lipid aldehydes and their glutathione conjugates with more than 1000-fold efficiency (Km aldehydes 5-30 µM) relative to glucose. Acrolein, a major endogenous lipid peroxidation product as well as a component of environmental pollutants and cigarette smoke, is known to be involved in various pathologies including atherosclerosis, airway inflammation, COPD, and age-related disorders, but the mechanism of acrolein-induced cytotoxicity is not clearly understood. We have investigated the role of AR in acrolein-induced cytotoxicity in primary human small airway epithelial cells (SAECs). Exposure of SAECs to varying concentrations of acrolein caused cell death in a concentration- and time-dependent manner. AR inhibition by fidarestat prevented the low-dose (5-10 µM) but not the high-dose (>10 µM) acrolein-induced SAEC death. AR inhibition protected SAECs from low-dose (5 µM) acrolein-induced cellular reactive oxygen species (ROS). Inhibition of acrolein-induced apoptosis by fidarestat was confirmed by decreased condensation of nuclear chromatin, DNA fragmentation, comet tail moment, and annexin V fluorescence. Further, fidarestat inhibited acrolein-induced translocation of the proapoptotic proteins Bax and Bad from the cytosol to the mitochondria and that of Bcl2 and BclXL from the mitochondria to the cytosol. Acrolein-induced cytochrome c release from mitochondria was also prevented by AR inhibition. The mitogen-activated protein kinases (MAPKs), such as extracellular signal-regulated kinases 1 and 2, stress-activated protein kinase/c-Jun NH2-terminal kinase, and p38MAPK, and c-Jun were transiently activated in airway epithelial cells by acrolein in a concentration- and time-dependent fashion, which was significantly prevented by AR inhibition. These results suggest that AR inhibitors could prevent acrolein-induced cytotoxicity in the lung epithelial cells.

  17. Occupational asthma due to formaldehyde.

    PubMed Central

    Burge, P S; Harries, M G; Lam, W K; O'Brien, I M; Patchett, P A

    1985-01-01

    Bronchial provocation studies on 15 workers occupationally exposed to formaldehyde are described. The results show that formaldehyde exposure can cause asthmatic reactions, and suggest that these are sometimes due to hypersensitivity and sometimes to a direct irritant effect. Three workers had classical occupational asthma caused by formaldehyde fumes, which was likely to be due to hypersensitivity, with late asthmatic reactions following formaldehyde exposure. Six workers developed immediate asthmatic reactions, which were likely to be due to a direct irritant effect as the reactions were shorter in duration than those seen after soluble allergen exposure and were closely related to histamine reactivity. The breathing zone concentrations of formaldehyde required to elicit these irritant reactions (mean 4.8 mg/m3) were higher than those encountered in buildings recently insulated with urea formaldehyde foam, but within levels sometimes found in industry. Images PMID:4023975

  18. Formaldehyde exposure in nonoccupational environments

    SciTech Connect

    Dally, K.A.; Hanahan, L.P.; Woodbury, M.A.; Kanarek, M.S.

    1981-01-01

    Free formaldehyde may be released from wood products and foam insulation where urea-formaldehyde resins have been used. From January, 1978 to November, 1979, 100 structures were investigated by the Wisconsin Division of Health after receiving complaints of health problems from occupants. Air samples were collected in midget impingers and analyzed for formaldehyde content by the chromotropic acid procedure. Health information was obtained from the occupants via questionnaires. Mean formaldehyde concentrations observed ranged from below the limit of detection to 3.68 ppm. Eye irritation, burning eyes, runny nose, dry or sore throat, headache, and cough were the primary symptoms which were reported by the occupants. Statistically significant associations were seen between formaldehyde levels and age of home/building materials. Observations presented suggest nonoccupational, indoor environmental exposure to formaldehyde is significant and may reach levels which exceed occupational exposure standards.

  19. Production of carbon-13-labeled cadaverine by engineered Corynebacterium glutamicum using carbon-13-labeled methanol as co-substrate.

    PubMed

    Leßmeier, Lennart; Pfeifenschneider, Johannes; Carnicer, Marc; Heux, Stephanie; Portais, Jean-Charles; Wendisch, Volker F

    2015-12-01

    Methanol, a one-carbon compound, can be utilized by a variety of bacteria and other organisms as carbon and energy source and is regarded as a promising substrate for biotechnological production. In this study, a strain of non-methylotrophic Corynebacterium glutamicum, which was able to produce the polyamide building block cadaverine as non-native product, was engineered for co-utilization of methanol. Expression of the gene encoding NAD+-dependent methanol dehydrogenase (Mdh) from the natural methylotroph Bacillus methanolicus increased methanol oxidation. Deletion of the endogenous aldehyde dehydrogenase genes ald and fadH prevented methanol oxidation to carbon dioxide and formaldehyde detoxification via the linear formaldehyde dissimilation pathway. Heterologous expression of genes for the key enzymes hexulose-6-phosphate synthase and 6-phospho-3-hexuloisomerase of the ribulose monophosphate (RuMP) pathway in this strain restored growth in the presence of methanol or formaldehyde, which suggested efficient formaldehyde detoxification involving RuMP key enzymes. While growth with methanol as sole carbon source was not observed, the fate of 13C-methanol added as co-substrate to sugars was followed and the isotopologue distribution indicated incorporation into central metabolites and in vivo activity of the RuMP pathway. In addition, 13C-label from methanol was traced to the secreted product cadaverine. Thus, this synthetic biology approach led to a C. glutamicum strain that converted the non-natural carbon substrate methanol at least partially to the non-native product cadaverine.

  20. Identification of the Active Species in Photochemical Hole Scavenging Reactions of Methanol on TiO2

    SciTech Connect

    Shen, Mingmin; Henderson, Michael A.

    2011-11-03

    Molecular and dissociative methanol adsorption species were prepared on rutile TiO2(110) surfaces to study photocatalytic oxidation of methanol in ultrahigh vacuum (UHV) using temperature-programmed desorption (TPD). Adsorbed methoxy groups (CH3O-) were found to be the photoactive form of adsorbed methanol converted to adsorbed formaldehyde and a surface OH group by hole-mediated C-H bond cleavage. These results suggest that adsorbed methoxy is the effective hole scavenger in photochemical reactions involving methanol.

  1. Scaffoldless engineered enzyme assembly for enhanced methanol utilization

    DOE PAGES

    Price, J. Vincent; Chen, Long; Whitaker, W. Brian; Papoutsakis, Eleftherios; Chen, Wilfred

    2016-10-24

    Methanol is an important feedstock derived from natural gas and can be chemically converted into commodity and specialty chemicals at high pressure and temperature. Although biological conversion of methanol can proceed at ambient conditions, there is a dearth of engineered microorganisms that use methanol to produce metabolites. In nature, methanol dehydrogenase (Mdh), which converts methanol to formaldehyde, highly favors the reverse reaction. Thus, efficient coupling with the irreversible sequestration of formaldehyde by 3-hexulose-6-phosphate synthase (Hps) and 6-phospho-3-hexuloseisomerase (Phi) serves as the key driving force to pull the pathway equilibrium toward central metabolism. An emerging strategy to promote efficient substrate channelingmore » is to spatially organize pathway enzymes in an engineered assembly to provide kinetic driving forces that promote carbon flux in a desirable direction. Here, we report a scaffoldless, self-assembly strategy to organize Mdh, Hps, and Phi into an engineered supramolecular enzyme complex using an SH3–ligand interaction pair, which enhances methanol conversion to fructose-6-phosphate (F6P). To increase methanol consumption, an “NADH Sink” was created using Escherichia coli lactate dehydrogenase as an NADH scavenger, thereby preventing reversible formaldehyde reduction. Combination of the two strategies improved in vitro F6P production by 97-fold compared with unassembled enzymes. The beneficial effect of supramolecular enzyme assembly was also realized in vivo as the engineered enzyme assembly improved whole-cell methanol consumption rate by ninefold. This approach will ultimately allow direct coupling of enhanced F6P synthesis with other metabolic engineering strategies for the production of many desired metabolites from methanol.« less

  2. High Resolution Formaldehyde Photochemistry

    NASA Astrophysics Data System (ADS)

    Ernest, C. T.; Bauer, D.; Hynes, A. J.

    2010-12-01

    Formaldehyde (HCHO) is the most abundant and most important organic carbonyl compound in the atmosphere. The sources of formaldehyde are the oxidation of methane, isoprene, acetone, and other volatile organic compounds (VOCs); fossil fuel combustion; and biomass burning. The dominant loss mechanism for formaldehyde is photolysis which occurs via two pathways: (R1) HCHO + hv → HCO + H (R2) HCHO + hv → H2 + CO The first pathway (R1) is referred to as the radical channel, while the second pathway (R2) is referred to as the molecular channel. The products of both pathways play a significant role in atmospheric chemistry. The CO that is produced in the molecular channel undergoes further oxidation to produce CO2. Under atmospheric conditions, the H atom and formyl radical that are produced in the radical channel undergo rapid reactions with O2 to produce the hydroperoxyl radical (HO2) via (R3) and (R4). (R3) HCO + O2 → HO2 + CO (R4) H + O2 → HO2 Thus, for every photon absorbed, the photolysis of formaldehyde can contribute one CO2 molecule to the global greenhouse budget or two HO2 radicals to the tropospheric HOx (OH + HO2) cycle. The HO2 radicals produced during formaldehyde photolysis have also been implicated in the formation of photochemical smog. The HO2 radicals act as radical chain carriers and convert NO to NO2, which ultimately results in the catalytic production of O3. Constraining the yield of HO2 produced via HCHO photolysis is essential for improving tropospheric chemistry models. In this study, both the absorption cross section and the quantum yield of the radical channel (R1) were measured at high resolution over the tropospherically relevant wavelength range 304-330 nm. For the cross section measurements a narrow linewidth Nd:YAG pumped dye laser was used with a multi-pass cell. Partial pressures of HCHO were kept below 0.3 torr. Simultaneous measurement of OH LIF in a flame allowed absolute calibration of the wavelength scale. Pressure

  3. UTILIZING THE PAKS METHOD FOR MEASURING ACROLEIN AND OTHER ALDEHYDES IN DEARS

    EPA Science Inventory

    Acrolein is a hazardous air pollutant of high priority due to its high irritation potency and other potential adverse health effects. However, a reliable method is currently unavailable for measuring airborne acrolein at typical environmental levels. In the Detroit Exposure and A...

  4. Indoor acrolein emission and decay rates resulting from domestic cooking events

    NASA Astrophysics Data System (ADS)

    Seaman, Vincent Y.; Bennett, Deborah H.; Cahill, Thomas M.

    2009-12-01

    Acrolein (2-propenal) is a common constituent of both indoor and outdoor air, can exacerbate asthma in children, and may contribute to other chronic lung diseases. Recent studies have found high indoor levels of acrolein and other carbonyls compared to outdoor ambient concentrations. Heated cooking oils produce considerable amounts of acrolein, thus cooking is likely an important source of indoor acrolein. A series of cooking experiments were conducted to determine the emission rates of acrolein and other volatile carbonyls for different types of cooking oils (canola, soybean, corn and olive oils) and deep-frying different food items. Similar concentrations and emission rates of carbonyls were found when different vegetable oils were used to deep-fry the same food product. The food item being deep-fried was generally not a significant source of carbonyls compared to the cooking oil. The oil cooking events resulted in high concentrations of acrolein that were in the range of 26.4-64.5 μg m -3. These concentrations exceed all the chronic regulatory exposure limits and many of the acute exposure limits. The air exchange rate and the decay rate of the carbonyls were monitored to estimate the half-life of the carbonyls. The half-life for acrolein was 14.4 ± 2.6 h, which indicates that indoor acrolein concentrations can persist for considerable time after cooking in poorly-ventilated homes.

  5. Ambient acrolein concentrations in coastal, remote, and urban regions in California.

    PubMed

    Cahill, Thomas M

    2014-01-01

    Acrolein (2-propenal) is a reactive chemical that is very toxic and has many sources. Acrolein is commonly detected in the atmosphere, but understanding the ambient concentrations of this compound has been hampered by analytical difficulties. The objective of this research was to utilize an analytical method specifically designed for acrolein to determine acrolein concentrations in remote regions. The purpose was to determine the natural background concentrations of acrolein which were simply lacking in the literature. In addition, rural and urban areas were sampled to determine the degree of anthropogenic enrichment in polluted environments. The results from the coastal and remote inland areas suggest that the median natural summertime background of acrolein was near 40 ng/m(3), which was higher than the Environmental Protection Agency's Reference Concentration (RfC) of 20 ng/m(3). Acrolein concentrations in urban areas were approximately 3- to 8-fold higher than background concentrations, which was a lower degree of urban enrichment than expected. The results suggest that additional research is needed to understand the natural background concentrations of acrolein.

  6. Acrolein induces Alzheimer's disease-like pathologies in vitro and in vivo.

    PubMed

    Huang, Ying-Juan; Jin, Ming-Hua; Pi, Rong-Biao; Zhang, Jun-Jie; Ouyang, Ying; Chao, Xiao-Juan; Chen, Mei-Hui; Liu, Pei-Qing; Yu, Jian-Chen; Ramassamy, Charles; Dou, Juan; Chen, Xiao-Hong; Jiang, Yi-Ming; Qin, Jian

    2013-03-13

    The pathologic mechanisms of Alzheimer's disease (AD) have not been fully uncovered. Acrolein, a ubiquitous dietary pollutant and by-product of oxidative stress, can induce cytotoxicity in neurons, which might play an important role in the etiology of AD. Here, we examined the effects of Acrolein on the AD pathologies in vitro and in vivo. We found Acrolein induced HT22 cells death in concentration- and time-dependent manners. Interestingly, Acrolein increased proteins' levels of amyloid precursor protein (APP), β-secretase (BACE-1) and the amyloid β-peptide transporter receptor for advanced glycation end products, and decreased A-disintegrin and metalloprotease (ADAM) 10 levels. In vivo, chronic oral exposure to Acrolein (2.5 mg/kg/day by intragastric gavage for 8 weeks) induced mild cognitive declination and pyknosis/atrophy of hippocampal neurons. The activity of superoxide dismutase was down-regulated while the level of malondialdehyde was up-regulated in rat brain. Moreover, Acrolein resulted in activation of astrocytes, up-regulation of BACE-1 in cortex and down-regulation of ADAM-10 in hippocampus and cortex. Taken together, our findings suggest that exposure to Acrolein induces AD-like pathology in vitro and in vivo. Scavenging Acrolein might be beneficial for the therapy of AD.

  7. 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...

  8. METHANOL: A POTENTIAL SOURCE OF ATMOSPHERIC FORMALDEHYDE. (R825257)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  9. Residual formaldehyde after low-temperature steam and formaldehyde sterilization

    PubMed Central

    Gibson, G. L.; Johnston, H. P.; Turkington, V. E.

    1968-01-01

    The levels of formaldehyde remaining in various articles have been estimated immediately after a low-temperature steam and formaldehyde sterilizing process and after various periods of aeration. These levels have been compared with the levels of ethylene oxide remaining after exposure to an ethylene oxide sterilizing process. In rubber and polythene and a plastic, formaldehyde levels are low and slowly fall even further. Ethylene oxide levels are relatively much higher even after seven days' aeration. It is not considered that the residual levels of formaldehyde in rubber, polythene, and a plastic should constitute a danger. Residual levels of formaldehyde in fabrics and paper are higher but this may be of value by giving a self-disinfecting action on storage. PMID:5717551

  10. Acrolein relaxes mouse isolated tracheal smooth muscle via a TRPA1-dependent mechanism.

    PubMed

    Cheah, Esther Y; Burcham, Philip C; Mann, Tracy S; Henry, Peter J

    2014-05-01

    Airway sensory C-fibres express TRPA1 channels which have recently been identified as a key chemosensory receptor for acrolein, a toxic and highly prevalent component of smoke. TRPA1 likely plays an intermediary role in eliciting a range of effects induced by acrolein including cough and neurogenic inflammation. Currently, it is not known whether acrolein-induced activation of TRPA1 produces other airway effects including relaxation of mouse airway smooth muscle. The aims of this study were to examine the effects of acrolein on airway smooth muscle tone in mouse isolated trachea, and to characterise the cellular and molecular mechanisms underpinning the effects of acrolein. Isometric tension recording studies were conducted on mouse isolated tracheal segments to characterise acrolein-induced relaxation responses. Release of the relaxant PGE₂ was measured by EIA to examine its role in the response. Use of selective antagonists/inhibitors permitted pharmacological characterisation of the molecular and cellular mechanisms underlying this relaxation response. Acrolein induced dose-dependent relaxation responses in mouse isolated tracheal segments. Importantly, these relaxation responses were significantly inhibited by the TRPA1 antagonists AP-18 and HC-030031, an NK₁ receptor antagonist RP-67580, and the EP₂ receptor antagonist PF-04418948, whilst completely abolished by the non-selective COX inhibitor indomethacin. Acrolein also caused rapid PGE₂ release which was suppressed by HC-030031. In summary, acrolein induced a novel bronchodilator response in mouse airways. Pharmacologic studies indicate that acrolein-induced relaxation likely involves interplay between TRPA1-expressing airway sensory C-fibres, NK₁ receptor-expressing epithelial cells, and EP₂-receptor expressing airway smooth muscle cells.

  11. Role of endoplasmic reticulum stress in acrolein-induced endothelial activation

    SciTech Connect

    Haberzettl, Petra; Vladykovskaya, Elena; Srivastava, Sanjay; Bhatnagar, Aruni

    2009-01-01

    Acrolein is a ubiquitous environmental pollutant and an endogenous product of lipid peroxidation. It is also generated during the metabolism of several drugs and amino acids. In this study, we examined the effects of acrolein on endothelial cells. Treatment of human umbilical vein endothelial cells (HUVECs) with 2 to 10 {mu}M acrolein led to an increase in the phosphorylation of eIF-2{alpha} within 10 to 30 min of exposure. This was followed by alternate splicing of XBP-1 mRNA and an increase in the expression of the endoplasmic reticulum (ER) chaperone genes Grp78 and Herp. Within 2-4 h of treatment, acrolein also increased the abundance and the nuclear transport of the transcription factors ATF3, AFT4, and CHOP. Acrolein-induced increase in ATF3 was prevented by treating the cells with the chemical chaperone - phenylbutyric acid (PBA). Treatment with acrolein increased phosphorylation of ERK1/2, p38, and JNK. The increase in JNK phosphorylation was prevented by PBA. Acrolein treatment led to activation and nuclear translocation of the transcription factor NF-{kappa}B and an increase in TNF-{alpha}, IL-6 and IL-8, but not MCP-1, mRNA. Increased expression of cytokine genes and NF-{kappa}B activation were not observed in cells treated with PBA. These findings suggest that exposure to acrolein induces ER stress and triggers the unfolded protein response and that NF-{kappa}B activation and stimulation of cytokine production by acrolein could be attributed, in part, to ER stress. Chemical chaperones of protein-folding may be useful in treating toxicological and pathological states associated with excessive acrolein exposure or production.

  12. Acrolein involvement in sensory and behavioral hypersensitivity following spinal cord injury in the rat.

    PubMed

    Due, Michael R; Park, Jonghyuck; Zheng, Lingxing; Walls, Michael; Allette, Yohance M; White, Fletcher A; Shi, Riyi

    2014-03-01

    Growing evidence suggests that oxidative stress, as associated with spinal cord injury (SCI), may play a critical role in both neuroinflammation and neuropathic pain conditions. The production of the endogenous aldehyde acrolein, following lipid peroxidation during the inflammatory response, may contribute to peripheral sensitization and hyperreflexia following SCI via the TRPA1-dependent mechanism. Here, we report that there are enhanced levels of acrolein and increased neuronal sensitivity to the aldehyde for at least 14 days after SCI. Concurrent with injury-induced increases in acrolein concentration is an increased expression of TRPA1 in the lumbar (L3-L6) sensory ganglia. As proof of the potential pronociceptive role for acrolein, intrathecal injections of acrolein revealed enhanced sensitivity to both tactile and thermal stimuli for up to 10 days, supporting the compound's pro-nociceptive functionality. Treatment of SCI animals with the acrolein scavenger hydralazine produced moderate improvement in tactile responses as well as robust changes in thermal sensitivity for up to 49 days. Taken together, these data suggest that acrolein directly modulates SCI-associated pain behavior, making it a novel therapeutic target for preclinical and clinical SCI as an analgesic. Following spinal cord injury (SCI), acrolein involvement in neuropathic pain is likely through direct activation and elevated levels of pro-nociceptive channel TRPA1. While acrolein elevation correlates with neuropathic pain, suppression of this aldehyde by hydralazine leads to an analgesic effect. Acrolein may serve as a novel therapeutic target for preclinical and clinical SCI to relieve both acute and chronic post-SCI neuropathic pain.

  13. ROLE OF ENDOPLASMIC RETICULUM STRESS IN ACROLEIN-INDUCED ENDOTHELIAL ACTIVATION

    PubMed Central

    Haberzettl, Petra; Vladykovskaya, Elena; Srivastava, Sanjay; Bhatnagar, Aruni

    2010-01-01

    Acrolein is a ubiquitous environmental pollutant and an endogenous product of lipid peroxidation. It is also generated during the metabolism of several drugs and amino acids. In this study, we examined the effects of acrolein on endothelial cells. Treatment of human umbilical vein endothelial cells (HUVECs) with 2 to 10 μM acrolein led to an increase in the phosphorylation of eIF-2α within 10 to 30 min of exposure. This was followed by alternate splicing of XBP-1 mRNA and an increase in the expression of the endoplasmic reticulum (ER) chaperone genes Grp78 and Herp. Within 2–4 h of treatment, acrolein also increased the abundance and the nuclear transport of the transcription factors ATF3, AFT4, and CHOP. Acrolein-induced increase in ATF3 was prevented by treating the cells with the chemical chaperone – phenylbutryic acid (PBA). Treatment with acrolein increased phosphorylation of ERK1/2, p38, and JNK. The increase in JNK phosphorylation was prevented by PBA. Acrolein treatment led to the activation and nuclear translocation of the transcription factor NF-κB and an increase in TNF-α, IL-6 and IL-8, but not MCP-1, mRNA. Increased synthesis of cytokine genes and NF-κB activation were not observed in cells treated with PBA. These findings suggest that exposure to acrolein induces ER stress and triggers the unfolded protein response and that NF-κB activation and stimulation of cytokine production by acrolein could be attributed, in part, to ER stress. Chemical chaperones of protein-folding may be useful in treating toxicological and pathological states associated with excessive acrolein exposure or production. PMID:18951912

  14. Electrochemical conversion of carbon dioxide to methanol with the assistance of formate dehydrogenase and methanol dehydrogenase as biocatalysts

    SciTech Connect

    Kuwabata, Susumu; Tsuda, Ryo; Yoneyama, Hiroshi )

    1994-06-15

    Electrolysis at potentials between -0.7 and -0.9 V vs SCE of carbon dioxide-saturated phosphate buffer solutions (pH7) containing formate dehydrogenase (FDH) and either methyl viologen (MV[sup 2+]) or pyrroloquinolinequinone (PQQ) as an electron mediator yielded formate with current efficiencies as high as 90%. The enzyme was durable as long as the electrolysis was carried out in the dark. Electrolysis of phosphate buffer solutions containing sodium formate in the presence of methanol dehydrogenase (MDH) and MV[sup 2+] at -0.7 V vs SCE yielded formaldehyde if the concentration of the enzyme used was low, whereas both formaldehyde and methanol were produced for relatively high concentrations of the enzyme where the methanol production began to occur when the formaldehyde produced accumulated. The use of PQQ in place of MV[sup 2+] as the electron mediator exclusively produced methanol alone after some induction period in the electrolysis. On the basis of these results, successful attempts have been made to reduce carbon dioxide to methanol with cooperative assistance of FDH and MDH in the presence of PQQ as the electron mediator. The role of enzyme and mediator in these reduction processes is discussed in detail. 34 refs., 10 figs., 2 tabs.

  15. Acrolein, an α,β-unsaturated carbonyl, inhibits both growth and PSII activity in the cyanobacterium Synechocystis sp. PCC 6803.

    PubMed

    Shimakawa, Ginga; Iwamoto, Tatsuya; Mabuchi, Tomohito; Saito, Ryota; Yamamoto, Hiroshi; Amako, Katsumi; Sugimoto, Toshio; Makino, Amane; Miyake, Chikahiro

    2013-01-01

    In this study, we sought to determine whether and how an α,β-unsaturated carbonyl, acrolein, can inhibit the growth of the cyanobacterium Synechocystis sp. PCC6803 (S. 6803). Treatment of S. 6803 with 200 µM acrolein for 3 d significantly and irreversibly inhibited its growth. To elucidate the inhibitory mechanism, we examined the effects of acrolein on photosynthesis. In contrast to dark conditions, the addition of acrolein to S. 6803 under conditions of illumination lowered the CO₂-dependent O₂ evolution rate (photosynthetic activity). Furthermore, treatment with acrolein lowered the activity reducing dimethyl benzoquinone in photosystem II (PSII). Acrolein also suppressed the reduction rate for the oxidized form of the reaction center chlorophyll of photosystem I (PSI), P700. These results indicate that acrolein inhibited PSII activity in thylakoid membranes. The addition of 200 µM acrolein to the illuminated S. 6803 cells gradually increased the steady-state level (Fs) of Chl fluorescence and decreased the quantum yield of PSII. These results suggested that acrolein damaged the acceptor side of PSII. On the other hand, acrolein did not inhibit respiration. From the above results, we gained insight into the metabolism of acrolein and its physiological effects in S. 6803.

  16. 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.

  17. The methods of formaldehyde emission testing of engine: A review

    NASA Astrophysics Data System (ADS)

    Zhang, Chunhui; Geng, Peng; Cao, Erming; Wei, Lijiang

    2015-12-01

    A number of measurements have been provided to detect formaldehyde in the atmosphere, but there are no clear unified standards in engine exhaust. Nowadays, formaldehyde, an unregulated emission from methanol engine, has been attracting increasing attention by researchers. This paper presents the detection techniques for formaldehyde emitted from the engines applied in recent market, introducing the approaches in terms of unregulated emission tests of formaldehyde, which involved gas chromatography, liquid chromatography, chromatography-mass spectrometry, chromatography-spectrum, Fourier infrared spectroscopy and spectrophotometry. The author also introduces the comparison regarding to the advantages of the existing detection techniques based on the principle, to compare with engine exhaust sampling method, the treatment in advance of detection, obtaining approaches accessing to the qualitative and quantitative analysis of chromatograms or spectra. The accuratest result obtained was chromatography though it cannot be used continuously. It also can be utilized to develop high requirements of emissions and other regulations. Fourier infrared spectroscopy has the advantage of continuous detection for a variety of unregulated emissions and can be applied to the bench in variable condition. However, its accuracy is not as good as chromatography. As the conclusion, a detection technique is chosen based on different requirements.

  18. Methanol may function as a cross-kingdom signal.

    PubMed

    Dorokhov, Yuri L; Komarova, Tatiana V; Petrunia, Igor V; Kosorukov, Vyacheslav S; Zinovkin, Roman A; Shindyapina, Anastasia V; Frolova, Olga Y; Gleba, Yuri Y

    2012-01-01

    Recently, we demonstrated that leaf wounding results in the synthesis of pectin methylesterase (PME), which causes the plant to release methanol into the air. Methanol emitted by a wounded plant increases the accumulation of methanol-inducible gene mRNA and enhances antibacterial resistance as well as cell-to-cell communication, which facilitates virus spreading in neighboring plants. We concluded that methanol is a signaling molecule involved in within-plant and plant-to-plant communication. Methanol is considered to be a poison in humans because of the alcohol dehydrogenase (ADH)-mediated conversion of methanol into toxic formaldehyde. However, recent data showed that methanol is a natural compound in normal, healthy humans. These data call into question whether human methanol is a metabolic waste product or whether methanol has specific function in humans. Here, to reveal human methanol-responsive genes (MRGs), we used suppression subtractive hybridization cDNA libraries of HeLa cells lacking ADH and exposed to methanol. This design allowed us to exclude genes involved in formaldehyde and formic acid detoxification from our analysis. We identified MRGs and revealed a correlation between increases in methanol content in the plasma and changes in human leukocyte MRG mRNA levels after fresh salad consumption by volunteers. Subsequently, we showed that the methanol generated by the pectin/PME complex in the gastrointestinal tract of mice induces the up- and downregulation of brain MRG mRNA. We used an adapted Y-maze to measure the locomotor behavior of the mice while breathing wounded plant vapors in two-choice assays. We showed that mice prefer the odor of methanol to other plant volatiles and that methanol changed MRG mRNA accumulation in the mouse brain.We hypothesize that the methanol emitted by wounded plants may have a role in plant-animal signaling. The known positive effect of plant food intake on human health suggests a role for physiological methanol in

  19. Methanol may function as a cross-kingdom signal.

    PubMed

    Dorokhov, Yuri L; Komarova, Tatiana V; Petrunia, Igor V; Kosorukov, Vyacheslav S; Zinovkin, Roman A; Shindyapina, Anastasia V; Frolova, Olga Y; Gleba, Yuri Y

    2012-01-01

    Recently, we demonstrated that leaf wounding results in the synthesis of pectin methylesterase (PME), which causes the plant to release methanol into the air. Methanol emitted by a wounded plant increases the accumulation of methanol-inducible gene mRNA and enhances antibacterial resistance as well as cell-to-cell communication, which facilitates virus spreading in neighboring plants. We concluded that methanol is a signaling molecule involved in within-plant and plant-to-plant communication. Methanol is considered to be a poison in humans because of the alcohol dehydrogenase (ADH)-mediated conversion of methanol into toxic formaldehyde. However, recent data showed that methanol is a natural compound in normal, healthy humans. These data call into question whether human methanol is a metabolic waste product or whether methanol has specific function in humans. Here, to reveal human methanol-responsive genes (MRGs), we used suppression subtractive hybridization cDNA libraries of HeLa cells lacking ADH and exposed to methanol. This design allowed us to exclude genes involved in formaldehyde and formic acid detoxification from our analysis. We identified MRGs and revealed a correlation between increases in methanol content in the plasma and changes in human leukocyte MRG mRNA levels after fresh salad consumption by volunteers. Subsequently, we showed that the methanol generated by the pectin/PME complex in the gastrointestinal tract of mice induces the up- and downregulation of brain MRG mRNA. We used an adapted Y-maze to measure the locomotor behavior of the mice while breathing wounded plant vapors in two-choice assays. We showed that mice prefer the odor of methanol to other plant volatiles and that methanol changed MRG mRNA accumulation in the mouse brain.We hypothesize that the methanol emitted by wounded plants may have a role in plant-animal signaling. The known positive effect of plant food intake on human health suggests a role for physiological methanol in

  20. Outdoor smog-chamber experiments: reactivity of methanol exhaust

    SciTech Connect

    Jeffries, H.E.; Sexton, K.G.; Holleman, M.S.

    1985-09-01

    The purpose of the report was to provide an experimental smog-chamber database especially designed to test photochemical kinetics mechanisms that would be used to assess the effects of methanol fuel use in automobiles. The mechanisms would be used in urban air-quality control models to investigate the advantages of large-scale use of methanol fuel in automobiles. The smog-chamber experiments were performed during three summer months. They have been added to the existing UNC database for photochemical mechanism validation and testing, bringing the total number of dual experiments in the database to over 400. Three different hydrocarbon mixtures were used: a 13-component mixture representing synthetic automobile exhaust; an 18-component mixture representing synthetic urban ambient hydrocarbons; and a 14-component mixture derived from the synthetic automobile exhaust by the addition of n-butane. Three different synthetic methanol-exhaust mixtures were used: 80% methanol/10% formaldehyde; and 100% methanol.

  1. Modification and inactivation of Cu,Zn-superoxide dismutase by the lipid peroxidation product, acrolein

    PubMed Central

    Kang, Jung Hoon

    2013-01-01

    Acrolein is the most reactive aldehydic product of lipid peroxidation and is found to be elevated in the brain when oxidative stress is high. The effects of acrolein on the structure and function of human Cu,Zn-superoxide dismutase (SOD) were examined. When Cu,Zn-SOD was incubated with acrolein, the covalent crosslinking of the protein was increased, and the loss of enzymatic activity was increased in a dose-dependent manner. Reactive oxygen species (ROS) scavengers and copper chelators inhibited the acrolein-mediated Cu,Zn-SOD modification and the formation of carbonyl compound. The present study shows that ROS may play a critical role in acrolein-induced Cu,Zn-SOD modification and inactivation. When Cu,Zn-SOD that has been exposed to acrolein was subsequently analyzed by amino acid analysis, serine, histidine, arginine, threonine and lysine residues were particularly sensitive. It is suggested that the modification and inactivation of Cu,Zn-SOD by acrolein could be produced by more oxidative cell environments. [BMB Reports 2013; 46(11): 555-560] PMID:24152914

  2. CRITICAL ROLE OF ACROLEIN IN SECONDARY INJURY FOLLOWING EX VIVO SPINAL CORD TRAUMA

    PubMed Central

    Hamann, Kristin; Durkes, Abigail; Ouyang, Hui; Pond, Amber

    2008-01-01

    The pathophysiology of spinal cord injury (SCI) is characterized by the initial, primary injury followed by secondary injury processes in which oxidative stress is a critical component. Secondary injury processes not only exacerbate pathology at the site of primary injury, but also result in spreading of injuries to the adjacent, otherwise healthy tissue. The lipid peroxidation byproduct acrolein has been implicated as one potential mediator of secondary injury. In order to further and rigorously elucidate the role of acrolein in secondary injury, a unique ex vivo model is utilized to isolate the detrimental effects of mechanical injury from toxins such as acrolein that are produced endogenously following SCI. We demonstrate that: 1) acrolein-lys adducts are capable of diffusing from compressed tissue to adjacent, otherwise uninjured tissue; 2) secondary injury by itself produces significant membrane damage and increased superoxide production; and 3) these injuries are significantly attenuated by the acrolein scavenger hydralazine. Furthermore, hydralazine treatment results in significantly less membrane damage 2 hours following compression injury, but not immediately after. These findings support our hypothesis that, following SCI, acrolein is increased to pathologic concentrations, contributes significantly to secondary injury, and thus represents a novel target for scavenging to promote improved recovery. PMID:18710419

  3. Scavenging of Toxic Acrolein by Resveratrol and Hesperetin and Identification of Adducts.

    PubMed

    Wang, Weixin; Qi, Yajing; Rocca, James R; Sarnoski, Paul J; Jia, Aiqun; Gu, Liwei

    2015-11-01

    The objective of this study was to investigate the ability of resveratrol and hesperetin to scavenge acrolein at pH 7.4 and 37 °C. About 6.4 or 5.2% of acrolein remained after reaction with resveratrol or hesperetin for 12 h at equimolar concentrations. An acrolein-resveratrol adduct and two acrolein-hesperetin adducts were isolated. Their structures were elucidated using mass and NMR spectroscopy. Acrolein reacted with resveratrol at the C-2 and C-3 positions through nucleophilic addition and formed an additional heterocyclic ring. Two similar monoacrolein-conjugated adducts were identified for hesperetin. Spectroscopic data suggested each acrolein-hesperetin adduct was a mixture of four stereoisomers due to the existence of two chiral carbon atoms. Yield of adducts was low at pH 5.4 but increased at pH 7.4 and 8.4. Higher pH also promoted the formation of diacrolein adducts. Results suggest that resveratrol and hesperetin exert health benefits in part through neutralizing toxic acrolein in vivo.

  4. Modification and inactivation of Cu,Zn-superoxide dismutase by the lipid peroxidation product, acrolein.

    PubMed

    Kang, Jung Hoon

    2013-11-01

    Acrolein is the most reactive aldehydic product of lipid peroxidation and is found to be elevated in the brain when oxidative stress is high. The effects of acrolein on the structure and function of human Cu,Zn-superoxide dismutase (SOD) were examined. When Cu,Zn-SOD was incubated with acrolein, the covalent crosslinking of the protein was increased, and the loss of enzymatic activity was increased in a dose-dependent manner. Reactive oxygen species (ROS) scavengers and copper chelators inhibited the acrolein-mediated Cu,Zn-SOD modification and the formation of carbonyl compound. The present study shows that ROS may play a critical role in acrolein-induced Cu,Zn-SOD modification and inactivation. When Cu,Zn-SOD that has been exposed to acrolein was subsequently analyzed by amino acid analysis, serine, histidine, arginine, threonine and lysine residues were particularly sensitive. It is suggested that the modification and inactivation of Cu,Zn-SOD by acrolein could be produced by more oxidative cell environments.

  5. Effects of bioreactive acrolein from automotive exhaust gases on human cells in vitro.

    PubMed

    Jaganjac, Morana; Prah, Iva Ozana; Cipak, Ana; Cindric, Marina; Mrakovcic, Lidija; Tatzber, Franz; Ilincic, Petar; Rukavina, Vinko; Spehar, Branka; Vukovic, Jelena Parlov; Telen, Sanda; Uchida, Koji; Lulic, Zoran; Zarkovic, Neven

    2012-11-01

    Acrolein is a toxic unsaturated aldehyde and widespread environmental pollutant produced during lipid peroxidation and also by burning of tobacco or liquid fuels. Inhalation or dermal exposure to acrolein could be toxic to organisms. This very reactive aldehyde has a strong affinity for binding to proteins thus forming pathogenic protein-adducts. In the present study we have analyzed formation of bioreactive acrolein-protein adducts in bovine serum albumin solution exposed to exhaust gases of mineral diesel fuel and of mineral diesel fuel supplemented with different amounts of a novel diesel fuel additive denoted Ecodiesel (produced by a genuine procedure of recycling of plant oils used for food preparation). The effects of acrolein-protein adducts were tested on human microvascular endothelial cells and on human osteosarcoma cells that are sensitive to bioactivities of lipid peroxidation products. The results have shown a reduction of the bioreactive acrolein in exhaust gases when mineral diesel was supplemented with 5-20% Ecodiesel. Moreover, acrolein-protein adducts obtained from mineral diesel supplemented with Ecodiesel were less toxic than those obtained from mineral diesel alone. Thus, we assume that supplementing mineral diesel fuel with Ecodiesel would be of benefit for the use of renewable energy, for environment and for human health due to reduced environmental pollution with bioreactive acrolein.

  6. Origin, occurrence, and source emission rate of acrolein in residential indoor air.

    PubMed

    Seaman, Vincent Y; Bennett, Deborah H; Cahill, Thomas M

    2007-10-15

    Acrolein, a volatile, unsaturated aldehyde, is a known respiratory toxicant and one of the 188 most hazardous air pollutants identified by the U.S. EPA. A newly developed analytical method was used to determine residential indoor air concentrations of acrolein and other volatile aldehydes in nine homes located in three California counties (Los Angeles, Placer, Yolo). Average indoor air concentrations of acrolein were an order of magnitude higher than outdoor concentrations at the same time. All homes showed similar diurnal patterns in indoor air concentrations, with acrolein levels in evening samples up to 2.5 times higherthan morning samples. These increases were strongly correlated with temperature and cooking events, and homes with frequent, regular cooking activity had the highest baseline (morning) acrolein levels. High acrolein concentrations were also found in newly built, uninhabited homes and in emissions from lumber commonly used in home construction, suggesting indoor contributions from off-gassing and/or secondary formation. The results provide strong evidence that human exposure to acrolein is dominated by indoor air with little contribution from ambient outdoor air. PMID:17993132

  7. Formaldehyde impairs transepithelial sodium transport

    PubMed Central

    Cui, Yong; Li, Huiming; Wu, Sihui; Zhao, Runzhen; Du, Deyi; Ding, Yan; Nie, Hongguang; Ji, Hong-Long

    2016-01-01

    Unsaturated oxidative formaldehyde is a noxious aldehyde in cigarette smoke that causes edematous acute lung injury. However, the mechanistic effects of formaldehyde on lung fluid transport are still poorly understood. We examined how formaldehyde regulates human epithelial sodium channels (ENaC) in H441 and expressed in Xenopus oocytes and exposed mice in vivo. Our results showed that formaldehyde reduced mouse transalveolar fluid clearance in vivo. Formaldehyde caused a dose-dependent inhibition of amiloride-sensitive short-circuit Na+ currents in H441 monolayers and of αβγ-ENaC channel activity in oocytes. α-ENaC protein was reduced, whereas phosphorylation of the extracellular regulated protein kinases 1 and 2 (ERK1/2) increased significantly post exposure. Moreover, both α- and γ-ENaC transcripts were down-regulated. Reactive oxygen species (ROS) was elevated significantly by formaldehyde in addition to markedly augmented membrane permeability of oocytes. These data suggest that formaldehyde contributes to edematous acute lung injury by reducing transalveolar Na+ transport, through decreased ENaC activity and enhanced membrane depolarization, and by elevating ROS production over long-term exposure. PMID:27762337

  8. Molecularly Imprinted Polymer Nanoparticles for Formaldehyde Sensing with QCM

    PubMed Central

    Hussain, Munawar; Kotova, Kira; Lieberzeit, Peter A.

    2016-01-01

    Herein, we report on molecularly imprinted polymers (MIPs) for detecting formaldehyde vapors in air streams. A copolymer thin film consisting of styrene, methacrylic acid, and ethylene glycol dimethacrylate on quartz crystal microbalance (QCM) yielded a detection limit of 500 ppb formaldehyde in dry air. Surprisingly, these MIPs showed specific behavior when tested against a range of volatile organic compounds (VOCs), such as acetaldehyde, methanol, formic acid, and dichloromethane. Despite thus being a suitable receptor in principle, the MIPs were not useful for measurements at 50% humidity due to surface saturation by water. This was overcome by introducing primary amino groups into the polymer via allyl amine and by changing the coating morphology from thin film to nanoparticles. This led to the same limit of detection (500 ppb) and selectivity as before, but at the real-life conditions of 50% relative humidity. PMID:27376287

  9. Molecularly Imprinted Polymer Nanoparticles for Formaldehyde Sensing with QCM.

    PubMed

    Hussain, Munawar; Kotova, Kira; Lieberzeit, Peter A

    2016-01-01

    Herein, we report on molecularly imprinted polymers (MIPs) for detecting formaldehyde vapors in air streams. A copolymer thin film consisting of styrene, methacrylic acid, and ethylene glycol dimethacrylate on quartz crystal microbalance (QCM) yielded a detection limit of 500 ppb formaldehyde in dry air. Surprisingly, these MIPs showed specific behavior when tested against a range of volatile organic compounds (VOCs), such as acetaldehyde, methanol, formic acid, and dichloromethane. Despite thus being a suitable receptor in principle, the MIPs were not useful for measurements at 50% humidity due to surface saturation by water. This was overcome by introducing primary amino groups into the polymer via allyl amine and by changing the coating morphology from thin film to nanoparticles. This led to the same limit of detection (500 ppb) and selectivity as before, but at the real-life conditions of 50% relative humidity. PMID:27376287

  10. Acute Acrolein Exposure Induces Impairment of Vocal Fold Epithelial Barrier Function

    PubMed Central

    Zheng, Wei; Sivasankar, M. Preeti

    2016-01-01

    Acrolein is a ubiquitous pollutant abundant in cigarette smoke, mobile exhaust, and industrial waste. There is limited literature on the effects of acrolein on vocal fold tissue, although there are clinical reports of voice changes after pollutant exposures. Vocal folds are responsible for voice production. The overall objective of this study was to investigate the effects of acrolein exposure on viable, excised vocal fold epithelial tissue and to characterize the mechanism underlying acrolein toxicity. Vocal fold epithelia were studied because they form the outermost layer of the vocal folds and are a primary recipient of inhaled pollutants. Porcine vocal fold epithelia were exposed to 0, 50, 100, 500, 900 or 1300 μM of acrolein for 3 hours; the metabolic activity, epithelial resistance, epithelial permeability, tight junction protein (occludin and claudin 3) expression, cell membrane integrity and lipid peroxidation were investigated. The data demonstrated that acrolein exposure at 500 μM significantly reduced vocal fold epithelial metabolic activity by 27.2% (p≤0.001). Incubation with 100 μM acrolein caused a marked increase in epithelial permeability by 130.5% (p<0.05) and a reduction in transepithelial electrical resistance (TEER) by 180.0% (p<0.001). While the expression of tight junctional protein did not change in acrolein-treated samples, the cell membrane integrity was significantly damaged with a 45.6% increase of lipid peroxidation as compared to controls (p<0.05). Taken together, these data provide evidence that acute acrolein exposure impairs vocal fold epithelial barrier integrity. Lipid peroxidation-induced cell membrane damage may play an important role in reducing the barrier function of the epithelium. PMID:27643990

  11. Acute Acrolein Exposure Induces Impairment of Vocal Fold Epithelial Barrier Function.

    PubMed

    Liu, Xinxin; Zheng, Wei; Sivasankar, M Preeti

    2016-01-01

    Acrolein is a ubiquitous pollutant abundant in cigarette smoke, mobile exhaust, and industrial waste. There is limited literature on the effects of acrolein on vocal fold tissue, although there are clinical reports of voice changes after pollutant exposures. Vocal folds are responsible for voice production. The overall objective of this study was to investigate the effects of acrolein exposure on viable, excised vocal fold epithelial tissue and to characterize the mechanism underlying acrolein toxicity. Vocal fold epithelia were studied because they form the outermost layer of the vocal folds and are a primary recipient of inhaled pollutants. Porcine vocal fold epithelia were exposed to 0, 50, 100, 500, 900 or 1300 μM of acrolein for 3 hours; the metabolic activity, epithelial resistance, epithelial permeability, tight junction protein (occludin and claudin 3) expression, cell membrane integrity and lipid peroxidation were investigated. The data demonstrated that acrolein exposure at 500 μM significantly reduced vocal fold epithelial metabolic activity by 27.2% (p≤0.001). Incubation with 100 μM acrolein caused a marked increase in epithelial permeability by 130.5% (p<0.05) and a reduction in transepithelial electrical resistance (TEER) by 180.0% (p<0.001). While the expression of tight junctional protein did not change in acrolein-treated samples, the cell membrane integrity was significantly damaged with a 45.6% increase of lipid peroxidation as compared to controls (p<0.05). Taken together, these data provide evidence that acute acrolein exposure impairs vocal fold epithelial barrier integrity. Lipid peroxidation-induced cell membrane damage may play an important role in reducing the barrier function of the epithelium. PMID:27643990

  12. 1,N(2)-propanodeoxyguanosine adduct formation in aortic DNA following inhalation of acrolein.

    PubMed Central

    Penn, A; Nath, R; Pan, J; Chen, L; Widmer, K; Henk, W; Chung, F L

    2001-01-01

    Recent reports indicate that many of the cytotoxic and health-threatening components of environmental tobacco smoke (ETS) reside in the vapor phase of the smoke. We have reported previously that inhalation of 1,3-butadiene, a prominent vapor phase component of ETS, accelerates arteriosclerotic plaque development in cockerels. In this study we asked whether inhaled acrolein, a reactive aldehyde that is also a prominent vapor-phase component of ETS, damages artery-wall DNA and accelerates plaque development. Cockerels inhaled 0, 1, or 10 ppm acrolein mixed with HEPA-filtered air for 6 hr. Half were killed immediately (day 1 group) for detection of the stable, premutagenic 1,N(2)-propanodeoxyguanosine acrolein adduct (AdG3) in aortic DNA via a (32)P-postlabeling/HPLC method, and half were killed after 10 days (day 10 group) for indirect assessment of adduct repair. In the day 1 group, acrolein-DNA adducts were 5 times higher in the 1 and 10 ppm groups than in HEPA-filtered air controls. However, in the day 10 group, adduct levels in the 1 and 10 ppm acrolein groups were reduced to the control adduct level. For the plaque studies, cockerels inhaled 1 ppm acrolein (6 hr/day, 8 weeks), mixed with the same HEPA-filtered air inhaled by controls. Plaque development was measured blind by computerized morphometry. Unlike butadiene inhalation, acrolein inhalation did not accelerate plaque development. Thus, even though repeated exposure to acrolein alone has no effect on plaque size under the exposure conditions described here, a single, brief inhalation exposure to acrolein elicits repairable DNA damage to the artery wall. These results suggest that frequent exposure to ETS may lead to persistent artery-wall DNA damage and thus provide sites on which other ETS plaque accelerants can act. PMID:11333181

  13. Acrolein decreases endothelial cell migration and insulin sensitivity through induction of let-7a.

    PubMed

    O'Toole, Timothy E; Abplanalp, Wesley; Li, Xiaohong; Cooper, Nigel; Conklin, Daniel J; Haberzettl, Petra; Bhatnagar, Aruni

    2014-08-01

    Acrolein is a major reactive component of vehicle exhaust, and cigarette and wood smoke. It is also present in several food substances and is generated endogenously during inflammation and lipid peroxidation. Although previous studies have shown that dietary or inhalation exposure to acrolein results in endothelial activation, platelet activation, and accelerated atherogenesis, the basis for these effects is unknown. Moreover, the effects of acrolein on microRNA (miRNA) have not been studied. Using AGILENT miRNA microarray high-throughput technology, we found that treatment of cultured human umbilical vein endothelial cells with acrolein led to a significant (>1.5-fold) upregulation of 12, and downregulation of 15, miRNAs. Among the miRNAs upregulated were members of the let-7 family and this upregulation was associated with decreased expression of their protein targets, β3 integrin, Cdc34, and K-Ras. Exposure to acrolein attenuated β3 integrin-dependent migration and reduced Akt phosphorylation in response to insulin. These effects of acrolein on endothelial cell migration and insulin signaling were reversed by expression of a let-7a inhibitor. Also, inhalation exposure of mice to acrolein (1 ppm x 6 h/day x 4 days) upregulated let-7a and led to a decrease in insulin-stimulated Akt phosphorylation in the aorta. These results suggest that acrolein exposure has broad effects on endothelial miRNA repertoire and that attenuation of endothelial cell migration and insulin signaling by acrolein is mediated in part by the upregulation of let-7a. This mechanism may be a significant feature of vascular injury caused by inflammation, oxidized lipids, and exposure to environmental pollutants.

  14. Theoretical studies of acrolein hydrogenation on Au20 nanoparticle

    NASA Astrophysics Data System (ADS)

    Li, Zhe; Chen, Zhao-Xu; He, Xiang; Kang, Guo-Jun

    2010-05-01

    Gold nanoparticles play a key role in catalytic processes. We investigated the kinetics of stepwise hydrogenation of acrolein on Au20 cluster model and compared with that on Au(110) surface. The rate-limiting step barrier of CC reduction is about 0.5 eV higher than that of CO hydrogenation on Au(110) surface. On Au20 nanoparticle, however, the energy barrier of the rate-determining step for CC hydrogenation turns out to be slightly lower than the value for the CO reduction. The selectivity difference on the two substrate models are attributed to different adsorption modes of acrolein: via the CC on Au20, compared to through both CC and CO on Au(110). The preference switch implies that the predicted selectivity of competitive hydrogenation depends on substrate model sensitively, and particles with more low-coordinated Au atoms than flat surfaces are favorable for CC hydrogenation, which is in agreement with experimental result.

  15. Catalytic process for formaldehyde oxidation

    NASA Technical Reports Server (NTRS)

    Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); D'Ambrosia, Christine M. (Inventor)

    1996-01-01

    Disclosed is a process for oxidizing formaldehyde to carbon dioxide and water without the addition of energy. A mixture of formaldehyde and an oxidizing agent (e.g., ambient air containing formaldehyde) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

  16. Sporostatic and Sporocidal Properties of Aqueous Formaldehyde

    PubMed Central

    Trujillo, Ralph; David, Thomas J.

    1972-01-01

    Aqueous formaldehyde is shown to exert both sporostatic and sporocidal effects on Bacillus subtilis spores. The sporostatic effect is a result of the reversible inhibition of spore germination occasioned by aqueous formaldehyde; the sporocidal effect is due to temperature-dependent inactivation of these spores in aqueous formaldehyde. The physicochemical state of formaldehyde in solution provides a framework with which to interpret both the sporostatic and sporocidal properties of aqueous formaldehyde. PMID:4623282

  17. C1 Metabolism in Corynebacterium glutamicum: an Endogenous Pathway for Oxidation of Methanol to Carbon Dioxide

    PubMed Central

    Witthoff, Sabrina; Mühlroth, Alice

    2013-01-01

    Methanol is considered an interesting carbon source in “bio-based” microbial production processes. Since Corynebacterium glutamicum is an important host in industrial biotechnology, in particular for amino acid production, we performed studies of the response of this organism to methanol. The C. glutamicum wild type was able to convert 13C-labeled methanol to 13CO2. Analysis of global gene expression in the presence of methanol revealed several genes of ethanol catabolism to be upregulated, indicating that some of the corresponding enzymes are involved in methanol oxidation. Indeed, a mutant lacking the alcohol dehydrogenase gene adhA showed a 62% reduced methanol consumption rate, indicating that AdhA is mainly responsible for methanol oxidation to formaldehyde. Further studies revealed that oxidation of formaldehyde to formate is catalyzed predominantly by two enzymes, the acetaldehyde dehydrogenase Ald and the mycothiol-dependent formaldehyde dehydrogenase AdhE. The Δald ΔadhE and Δald ΔmshC deletion mutants were severely impaired in their ability to oxidize formaldehyde, but residual methanol oxidation to CO2 was still possible. The oxidation of formate to CO2 is catalyzed by the formate dehydrogenase FdhF, recently identified by us. Similar to the case with ethanol, methanol catabolism is subject to carbon catabolite repression in the presence of glucose and is dependent on the transcriptional regulator RamA, which was previously shown to be essential for expression of adhA and ald. In conclusion, we were able to show that C. glutamicum possesses an endogenous pathway for methanol oxidation to CO2 and to identify the enzymes and a transcriptional regulator involved in this pathway. PMID:24014532

  18. C1 metabolism in Corynebacterium glutamicum: an endogenous pathway for oxidation of methanol to carbon dioxide.

    PubMed

    Witthoff, Sabrina; Mühlroth, Alice; Marienhagen, Jan; Bott, Michael

    2013-11-01

    Methanol is considered an interesting carbon source in "bio-based" microbial production processes. Since Corynebacterium glutamicum is an important host in industrial biotechnology, in particular for amino acid production, we performed studies of the response of this organism to methanol. The C. glutamicum wild type was able to convert (13)C-labeled methanol to (13)CO2. Analysis of global gene expression in the presence of methanol revealed several genes of ethanol catabolism to be upregulated, indicating that some of the corresponding enzymes are involved in methanol oxidation. Indeed, a mutant lacking the alcohol dehydrogenase gene adhA showed a 62% reduced methanol consumption rate, indicating that AdhA is mainly responsible for methanol oxidation to formaldehyde. Further studies revealed that oxidation of formaldehyde to formate is catalyzed predominantly by two enzymes, the acetaldehyde dehydrogenase Ald and the mycothiol-dependent formaldehyde dehydrogenase AdhE. The Δald ΔadhE and Δald ΔmshC deletion mutants were severely impaired in their ability to oxidize formaldehyde, but residual methanol oxidation to CO2 was still possible. The oxidation of formate to CO2 is catalyzed by the formate dehydrogenase FdhF, recently identified by us. Similar to the case with ethanol, methanol catabolism is subject to carbon catabolite repression in the presence of glucose and is dependent on the transcriptional regulator RamA, which was previously shown to be essential for expression of adhA and ald. In conclusion, we were able to show that C. glutamicum possesses an endogenous pathway for methanol oxidation to CO2 and to identify the enzymes and a transcriptional regulator involved in this pathway.

  19. Adaptation to acrolein through upregulating the protection by glutathione in human bronchial epithelial cells: the materialization of the hormesis concept.

    PubMed

    Sthijns, Mireille M J P E; Randall, Matthew J; Bast, Aalt; Haenen, Guido R M M

    2014-04-18

    Acrolein is a thiol reactive compound present in cigarette smoke and plays a pivotal role in the deleterious effects of smoking. Acrolein causes toxicity in human bronchial epithelial cells in a dose dependent manner. GSH forms the first line of defense against acrolein-induced toxicity. At high doses of acrolein (⩾10 μM) the capacity of the cellular protection by GSH is overwhelmed and GSH is not able to quench all the acrolein, resulting in cytotoxicity. At a relatively low dose of acrolein (3 μM), no cytotoxicity is observed due to protection by GSH. Moreover we found that exposure to a low dose of acrolein protects cells against the toxic effect of a second higher dose of acrolein. The adaptation to acrolein is induced via Nrf2 mediated gene expression of γ-glutamylcysteine synthetase leading to elevated GSH levels. This upregulation of the protection by GSH demonstrates a hormetic response to acrolein. Hormesis is an adaptive or compensatory response induced by a relatively subtle challenge of homeostasis by a toxic compound. Insight into the mechanism of hormesis is mandatory for a more accurate societal regulation of toxic compounds.

  20. Acrolein in wine: importance of 3-hydroxypropionaldehyde and derivatives in production and detection.

    PubMed

    Bauer, Rolene; Cowan, Donald A; Crouch, Andrew

    2010-03-24

    Certain lactic acid bacteria strains belonging to the genus Lactobacillus have been implicated in the accumulation of 3-hydroxypropionaldehyde (3-HPA) during anaerobic glycerol fermentation. In aqueous solution 3-HPA undergoes reversible dimerization and hydration, resulting in an equilibrium state between different derivatives. Wine quality may be compromised by the presence of 3-HPA due to the potential for spontaneous conversion into acrolein under winemaking conditions. Acrolein is highly toxic and has been implicated in the development of bitterness in wine. Interconversion between 3-HPA derivatives and acrolein is a complex and highly dynamic process driven by hydration and dehydration reactions. Acrolein is furthermore highly reactive and its steady-state concentration in complex systems very low. As a result, analytical detection and quantification in solution is problematic. This paper reviews the biochemical and environmental conditions leading to accumulation of its precursor, 3-HPA. Recent advances in analytical detection are summarized, and the roles played by natural chemical derivatives are highlighted.

  1. Factors contributing to the ability of acrolein to scavenge corrosive hydrogen sulfide

    SciTech Connect

    Kissel, C.L.; Brady, J.L.; Gottry, N.; Meshishnek, M.J.; Preus, M.W.

    1985-10-01

    Acrolein can function under a variety of conditions as an effective hydrogen sulfide scavenger in oilfield waterflood systems. The scavenging ability is maximized in waters having a pH range of 6 through 8, a total dissolved solids level below 1%, and temperatures less than 149/sup 0/F (65/sup 0/C). At least 4 ppm acrolein is necessary to achieve sufficient reaction of each original 1 ppm hydrogen sulfide. This reaction requires about 2 to 20 minutes, depending on the nature of the system. Although sand, garnet, or diatomaceous earth filters do not affect the scavenging ability of acrolein, charcoal filters, large tanks, long pipelines, high-temperature Wemcos, and reboilers can produce diminished effects. Further diminished effects also can be produced when incompatible chemicals are used concurrently with acrolein. Some application techniques that can lessen or eliminate these adverse conditions are presented.

  2. Factors contributing to the ability of Acrolein to scavenge corrosive hydrogen sulfide

    SciTech Connect

    Kissel, C.L.; Brady, J.L.; Clifton, N.; Meshishnek, M.J.; Preus, M.W.

    1983-03-01

    Acrolein can function under a variety of conditions as an effective hydrogen sulfide scavenger in oil field water flood systems. The scavenging ability is maximized in waters having a pH range of 6-8, a total dissolved solids level below 1 percent, and temperatures less than 65/sup 0/C. At least 4 ppm acrolein is necessary to achieve sufficient reaction of each original 1 ppm hydrogen sulfide. This reaction requires about 2-20 minutes, depending on the nature of the system. Although sand, garnet, or diatomaceous earth filters do not affect the scavenging ability of acrolein, charcoal filters, large tanks, long pipelines, high temperature Wemcos, and reboilers can produce diminished effects. Further diminished effects can also be produced when incompatible chemicals are used concurrently with acrolein. Some application techniques are presented which can lessen or eliminate these adverse conditions.

  3. Acrolein activates matrix metalloproteinases by increasing reactive oxygen species in macrophages

    SciTech Connect

    O'Toole, Timothy E. Zheng Yuting; Hellmann, Jason; Conklin, Daniel J.; Barski, Oleg; Bhatnagar, Aruni

    2009-04-15

    Acrolein is a ubiquitous component of environmental pollutants such as automobile exhaust, cigarette, wood, and coal smoke. It is also a natural constituent of several foods and is generated endogenously during inflammation or oxidation of unsaturated lipids. Because increased inflammation and episodic exposure to acrolein-rich pollutants such as traffic emissions or cigarette smoke have been linked to acute myocardial infarction, we examined the effects of acrolein on matrix metalloproteinases (MMPs), which destabilize atherosclerotic plaques. Our studies show that exposure to acrolein resulted in the secretion of MMP-9 from differentiated THP-1 macrophages. Acrolein-treatment of macrophages also led to an increase in reactive oxygen species (ROS), free intracellular calcium ([Ca{sup 2+}]{sub i}), and xanthine oxidase (XO) activity. ROS production was prevented by allopurinol, but not by rotenone or apocynin and by buffering changes in [Ca{sup 2+}]{sub I} with BAPTA-AM. The increase in MMP production was abolished by pre-treatment with the antioxidants Tiron and N-acetyl cysteine (NAC) or with the xanthine oxidase inhibitors allopurinol or oxypurinol. Finally, MMP activity was significantly stimulated in aortic sections from apoE-null mice containing advanced atherosclerotic lesions after exposure to acrolein ex vivo. These observations suggest that acrolein exposure results in MMP secretion from macrophages via a mechanism that involves an increase in [Ca{sup 2+}]{sub I}, leading to xanthine oxidase activation and an increase in ROS production. ROS-dependent activation of MMPs by acrolein could destabilize atherosclerotic lesions during brief episodes of inflammation or pollutant exposure.

  4. Acrolein, a product of lipid peroxidation, inhibits glucose and glutamate uptake in primary neuronal cultures.

    PubMed

    Lovell, M A; Xie, C; Markesbery, W R

    2000-10-15

    Oxidative stress has been implicated in the pathogenesis of several neurodegenerative disorders including Alzheimer's disease (AD). Increased lipid peroxidation, decreased levels of polyunsaturated fatty acids, and increased levels of 4-hydroxynonenal (HNE), F(2)-isoprostanes, and F(4)-neuroprostanes are present in the brain in patients with AD. Acrolein, an alpha,beta-unsaturated aldehydic product of lipid peroxidation has been demonstrated to be approximately 100 times more reactive than HNE and is present in neurofibrillary tangles in the brain in AD. We recently demonstrated statistically significant elevated concentrations of extractable acrolein in the hippocampus/parahippocampal gyrus and amygdala in AD compared with age-matched control subjects. Concentrations of acrolein were two to five times those of HNE in the same samples. Treatment of hippocampal cultures with acrolein led to a time- and concentration-dependent decrease in cell survival as well as a concentration-dependent increase in intracellular calcium. In cortical neuron cultures, we now report that acrolein causes a concentration-dependent impairment of glutamate uptake and glucose transport in cortical neuron cultures. Treatment of cortical astrocyte cultures with acrolein led to the same pattern of impairment of glutamate uptake as observed in cortical neuron cultures. Collectively, these data demonstrate neurotoxicity mechanisms of arolein that might be important in the pathogenesis of neuron degeneration in AD.

  5. Prior exposure to acrolein accelerates pulmonary inflammation in influenza A-infected mice.

    PubMed

    Ong, Ferrer H C; Henry, Peter J; Burcham, Philip C

    2012-08-01

    The combustion product acrolein contributes to several smoke-related health disorders, but whether this immunomodulatory toxicant alters pulmonary susceptibility to viruses has received little attention. To study the effects of prior acrolein dosing on the severity of influenza A viral infection, male BALB/c mice received acrolein (1mg/kg) or saline (control) via oropharyngeal aspiration either 4- or 7-days prior to intranasal inoculation with either influenza A/PR/8/34 virus or vehicle. At 0, 2, 4 and 7 days post-inoculation, lung samples were assessed for histological changes while pulmonary inflammation was monitored by estimating immune cell numbers and cytokine levels in bronchoalveolar lavage fluid (BALF). After viral challenge, animals that were exposed to acrolein 4 days previously experienced greater weight loss and exhibited an accelerated inflammatory response at 2 days after viral inoculation. Thus compared to saline-pretreated, virus-challenged controls, BALF recovered from these mice contained higher numbers of macrophages and neutrophils in addition to increased levels of several inflammatory cytokines, including IL-1α, IL-1β, IL-6, TNF, IFN-γ, KC, and MCP-1. The acrolein-induced increase in viral susceptibility was suppressed by the carbonyl scavenger bisulphite. These findings suggest acute acrolein intoxication "primes" the lung to mount an accelerated immune response to inhaled viruses.

  6. 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.

  7. A tailored catalyst for the sustainable conversion of glycerol to acrolein: mechanistic aspect of sequential dehydration.

    PubMed

    Yun, Danim; Kim, Tae Yong; Park, Dae Sung; Yun, Yang Sik; Han, Jeong Woo; Yi, Jongheop

    2014-08-01

    Developing a catalyst to resolve deactivation caused from coke is a primary challenge in the dehydration of glycerol to acrolein. An open-macropore-structured and Brønsted-acidic catalyst (Marigold-like silica functionalized with sulfonic acid groups, MS-FS) was synthesized for the stable and selective production of acrolein from glycerol. A high acrolein yield of 73% was achieved and maintained for 50 h in the presence of the MS-FS catalyst. The hierarchical structure of the catalyst with macropores was found to have an important effect on the stability of the catalyst because coke polymerization and pore blocking caused by coke deposition were inhibited. In addition, the behavior of 3-hydroxypropionaldehyde (3-HPA) during the sequential dehydration was studied using density functional theory (DFT) calculations because 3-HPA conversion is one of the main causes for coke formation. We found that the easily reproducible Brønsted acid sites in MS-FS permit the selective and stable production of acrolein. This is because the reactive intermediate (3-HPA) is readily adsorbed on the regenerated acid sites, which is essential for the selective production of acrolein during the sequential dehydration. The regeneration ability of the acid sites is related not only to the selective production of acrolein but also to the retardation of catalyst deactivation by suppressing the formation of coke precursors originating from 3-HPA degradation.

  8. 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.

  9. Acrolein stimulates the synthesis of IL-6 and C-reactive protein (CRP) in thrombosis model mice and cultured cells.

    PubMed

    Saiki, Ryotaro; Hayashi, Daisuke; Ikuo, Yukiko; Nishimura, Kazuhiro; Ishii, Itsuko; Kobayashi, Kaoru; Chiba, Kan; Toida, Toshihiko; Kashiwagi, Keiko; Igarashi, Kazuei

    2013-12-01

    Measurements of protein-conjugated acrolein (PC-Acro), IL-6, and C-reactive protein (CRP) in plasma were useful for identifying silent brain infarction with high sensitivity and specificity. The aim of this study was to determine whether acrolein causes increased production of IL-6 and CRP in thrombosis model mice and cultured cells. In mice with photochemically induced thrombosis, acrolein produced at the locus of infarction increased the level of IL-6 and then CRP in plasma. This was confirmed in cell culture systems - acrolein stimulated the production of IL-6 in mouse neuroblastoma Neuro-2a cells, mouse macrophage-like J774.1 cells, and human umbilical vein endothelial cells (HUVEC), and IL-6 in turn stimulated the production of CRP in human hepatocarcinoma cells. The level of IL-6 mRNA was increased by acrolein through an increase in phosphorylation of the transcription factors, c-Jun, and NF-κB p65. Furthermore, CRP stimulated IL-6 production in mouse macrophage-like J774.1 cells and HUVEC. IL-6 functioned as a protective factor against acrolein toxicity in Neuro-2a cells and HUVEC. These results show that acrolein stimulates the synthesis of IL-6 and CRP, which function as protecting factors against acrolein toxicity, and that the combined measurement of PC-Acro, IL-6, and CRP is effective for identification of silent brain infarction. The combined measurements of protein-conjugated acrolein (PC-Acro), IL-6, and C-reactive protein (CRP) in plasma were useful for identifying silent brain infarction. The aim of this study was to determine whether acrolein causes increased production of IL-6 and CRP, and indeed acrolein increased IL-6 synthesis and IL-6 in turn increased CRP synthesis. Furthermore, IL-6 decreased acrolein toxicity in several cell lines.

  10. Does formaldehyde induce aneuploidy?

    PubMed

    Speit, Günter; Kühner, Stefanie; Linsenmeyer, Regina; Schütz, Petra

    2011-11-01

    Formaldehyde (FA) was tested for a potential aneugenic activity in mammalian cells. We employed tests to discriminate between aneugenic and clastogenic effects in accordance with international guidelines for genotoxicity testing. The cytokinesis-block micronucleus test (CBMNT) in combination with fluorescence in situ hybridisation (FISH) with a pan-centromeric probe was performed with cultured human lymphocytes and the human A549 lung cell line. FA induced micronuclei (MN) in binuclear cells of both cell types under standard in vitro test conditions following the OECD guideline 487. FISH analysis revealed that the vast majority of induced MN were centromere negative, thus indicating a clastogenic effect. A similar result was obtained for MN induced by γ-irradiation, whereas the typical aneugens colcemid (COL) and vincristine (VCR) predominantly induced centromere-positive MN. Furthermore, COL and VCR clearly enhanced the MN frequency in mononuclear lymphocytes in the CBMNT, whereas such an effect was not observed for γ-irradiation and FA. In experiments with the Chinese hamster V79 cell line, the aneugens COL and VCR clearly increased the frequency of tetraploid second division metaphases, whereas FA did not cause such an effect. Altogether, our results confirm the clastogenicity of FA in cultured mammalian cells but exclude a significant aneugenic activity. PMID:21804075

  11. Acute systemic accumulation of acrolein in mice by inhalation at a concentration similar to that in cigarette smoke

    PubMed Central

    Tully, Melissa; Zheng, Lingxing; Acosta, Glen; Tian, Ran; Shi, Riyi

    2015-01-01

    Cigarette smoke is an important environmental factor associated with a wide array of public health concerns. Acrolein, a component of tobacco smoke and a known toxin to various cell types, may be a key pathological factor mediating the adverse effects linked with tobacco smoke. Although acrolein is known to accumulate in the respiratory system after acute nasal exposure, it is not clear if it accumulates systemically, and less is known in the nervous system. The aim of this study was to assess the degree of acrolein accumulation in the circulation and in the spinal cord following acute acrolein inhalation in mice. Using a laboratory-fabricated inhalation chamber, we found elevated urinary 3-HPMA, an acrolein metabolite, and increased acrolein adducts in the spinal cord after weeks of nasal exposure to acrolein at a concentration similar to that in tobacco smoke. The data indicated that acrolein is absorbed into the circulatory system and some enters the nervous system. It is expected that these findings may facilitate further studies to probe the pathological role of acrolein in the nervous system resulting from smoke and other external sources. PMID:25446876

  12. Inhibition of acrolein-stimulated MUC5AC expression by Platycodon grandiflorum root-derived saponin in A549 cells.

    PubMed

    Choi, Jae Ho; Hwang, Yong Pil; Han, Eun Hee; Kim, Hyung Gyun; Park, Bong Hwan; Lee, Hyun Sun; Park, Byung Keun; Lee, Young Chun; Chung, Young Chul; Jeong, Hye Gwang

    2011-09-01

    Mucin overproduction is a hallmark of chronic airway diseases such as chronic obstructive pulmonary disease. In this study, we investigated the inhibition of acrolein-induced expression of mucin 5, subtypes A and C (MUC5AC) by Changkil saponin (CKS) in A549 cells. Acrolein, a known toxin in tobacco smoke and an endogenous mediator of oxidative stress, increases the expression of airway MUC5AC, a major component of airway mucus. CKS, a Platycodon grandiflorum root-derived saponin, inhibited acrolein-induced MUC5AC expression and activity, through the suppression of NF-κB activation. CKS also repressed acrolein-induced phosphorylation of ERK1/2, JNK1/2, and p38MAPK, which are upstream signaling molecules that control MUC5AC expression. In addition, the MAPK inhibitors PD98059 (ERK1/2), SP600125 (JNK1/2), and SB203580 (p38 MAPK), and a PKC delta inhibitor (rottlerin; PKCδ) inhibited acrolein-induced MUC5AC expression and activity. CKS repressed acrolein-induced phosphorylation of PKCδ. Moreover, a reactive oxygen species (ROS) inhibitor, N-acetylcysteine, inhibited acrolein-induced MUC5AC expression and activity through the suppression of PKCδ and MAPK activation, and CKS repressed acrolein-induced ROS production. These results suggest that CKS suppresses acrolein-induced MUC5AC expression by inhibiting the activation of NF-κB via ROS-PKCδ-MAPK signaling. PMID:21664222

  13. Acute systemic accumulation of acrolein in mice by inhalation at a concentration similar to that in cigarette smoke.

    PubMed

    Tully, Melissa; Zheng, Lingxing; Acosta, Glen; Tian, Ran; Shi, Riyi

    2014-12-01

    Cigarette smoke is an important environmental factor associated with a wide array of public health concerns. Acrolein, a component of tobacco smoke and a known toxin to various cell types, may be a key pathological factor mediating the adverse effects linked with tobacco smoke. Although acrolein is known to accumulate in the respiratory system after acute nasal exposure, it is not clear if it accumulates systemically, and less is known in the nervous system. The aim of this study was to assess the degree of acrolein accumulation in the circulation and in the spinal cord following acute acrolein inhalation in mice. Using a laboratory-fabricated inhalation chamber, we found elevated urinary 3-HPMA, an acrolein metabolite, and increased acrolein adducts in the spinal cord after weeks of nasal exposure to acrolein at a concentration similar to that in tobacco smoke. The data indicated that acrolein is absorbed into the circulatory system and some enters the nervous system. It is expected that these findings may facilitate further studies to probe the pathological role of acrolein in the nervous system resulting from smoke and other external sources.

  14. Effect of additions of C/sub 2/-C/sub 4/ alcohols on the catalytic activity of silver in the oxidation of methanol

    SciTech Connect

    Kurina, L.N.; Zeile, L.E.; Filicheva, O.D.; Roznina, M.I.

    1988-02-20

    The authors give the results of a study of the partial oxidation of methanol on a pumice-silver catalyst in the presence of ethyl, isopropyl, and isobutyl alcohol impurities that are contained in the methanol feedstock. The choice of alcohols as the materials of the investigation is related to the fact that in the rectification of the methanol feedstock the recovered methanol-fusel oil-water fraction, containing up to 33% water, 5% ethanol, and up to 13% higher alcohols, is burned, i.e., is irretrievably lost for industry, while this valuable chemical raw material can be used for formaldehyde synthesis. The gaseous reaction products were analyzed for CO, CO/sub 2/, H/sub 2/, and O/sub 2/ contents; the amount of the obtained formaldehyde was determined by the sulfite method, the acidity of the formaldehyde solution was determined titrimetrically, and the content of the unreacted methanol was determined chromatographically. The results of the analysis were used to calculate the yields of formaldehyde and gases and the selectivity as the ratio of the amount of methanol consumed for formaldehyde formation to all the reacted methanol.

  15. Acrolein and chloroacetaldehyde: an examination of the cell and cell-free biomarkers of toxicity.

    PubMed

    MacAllister, Stephanie L; Martin-Brisac, Nicolas; Lau, Vincent; Yang, Kai; O'Brien, Peter J

    2013-02-25

    Cyclophosphamide and ifosfamide are two commonly used DNA-alkylating agents in cancer chemotherapy that undergo biotransformation to several toxic and non-toxic metabolites, including acrolein and chloroacetaldehyde (CAA). Acrolein and CAA toxicities occur by several different mechanisms, including ROS formation and protein damage (oxidation), however, these pathways of toxicity and protecting agents used to prevent them have yet to be compared and ranked in a single study. This research focused on the molecular targets of acrolein and CAA toxicities and strategies to decrease toxicities. Hepatocyte viability (cytotoxicity) was assessed using Trypan blue uptake; formation of reactive oxygen species (ROS) and endogenous H2O2 were also assessed in the hepatocyte model. In cell-free models (bovine serum albumin and hepatic microsomes), protein carbonylation was the measurement of toxicity. The present study demonstrated that acrolein was a more potent toxin than CAA for freshly isolated rat hepatocytes, bovine serum albumin and rat hepatic microsomes. Acrolein protein carbonylation was dependent on its concentration; as acrolein concentration increased, protein carbonylation increased in a linear trend, whereas, CAA deviated from the trend and did not cause protein carbonylation at lower concentrations (<400 μM). Aldehyde dehydrogenase (ALDH) is a major pathway for detoxifying pathway for CAA in hepatocytes, as a 3-fold increase in cytotoxicity occurred when cells were incubated with cyanamide, an ALDH inhibitor. Inhibiting ALDH or depleting GSH in hepatocytes increased cytotoxicity by about 3-fold in acrolein-treated hepatocytes. The overall effectiveness of protecting agents to prevent or suppress acrolein or CAA toxicities in cell and cell-free models were ranked in order of most effective to least effective: reducing agents (sodium borohydride, sodium bisulfite)>thiol-containing compounds (N-acetylcysteine, cysteine, glutathione, 2-mercaptoethane sulfonate [MESNA

  16. Formaldehyde exposures from tobacco smoke: a review.

    PubMed Central

    Godish, T

    1989-01-01

    Reports of formaldehyde levels in mainstream, sidestream, and environmental tobacco smoke from nine studies are reviewed. Considerable disparity exists between formaldehyde production rates determined from mainstream-sidestream studies and those reporting levels in environmental tobacco smoke. Tobacco smoke does not appear to increase vapor-phase formaldehyde levels significantly in indoor environments, but formaldehyde exposure in mainstream smoke may pose a risk of upper respiratory system cancer and increase the risk of cancer in smokers. PMID:2665532

  17. Formaldehyde exposures from tobacco smoke: A review

    SciTech Connect

    Godish, T.

    1989-08-01

    Reports of formaldehyde levels in mainstream, sidestream, and environmental tobacco smoke from nine studies are reviewed. Considerable disparity exists between formaldehyde production rates determined from mainstream-sidestream studies and those reporting levels in environmental tobacco smoke. Tobacco smoke does not appear to increase vapor-phase formaldehyde levels significantly in indoor environments, but formaldehyde exposure in mainstream smoke may pose a risk of upper respiratory system cancer and increase the risk of cancer in smokers. 18 references.

  18. Formaldehyde reactions in dark clouds.

    PubMed

    Sen, A D; Anicich, V G; Federman, S R

    1992-05-20

    The low-pressure reactions of formaldehyde (H2CO) with D+, D2+, D3+, and He+ have been studied by the ion cyclotron resonance technique. These reactions are potential loss processes for formaldehyde in cores of dark interstellar clouds. The deuterated reactants, which are easier to study experimentally, represent direct analogs for protons. Rate coefficients and branching ratios of product channels have been measured. Charge transfer is observed to be the dominant reaction of H2CO with D+, D2+, and He+ ions. Only the D3+ reaction exhibits a proton transfer channel. All reactions proceed at rate coefficients near the collision limit. Proton-deuteron exchange reactions were found to be inefficient processes in the formaldehyde system.

  19. Chaperone heat shock protein 90 mobilization and hydralazine cytoprotection against acrolein-induced carbonyl stress.

    PubMed

    Burcham, Philip C; Raso, Albert; Kaminskas, Lisa M

    2012-11-01

    Toxic carbonyls such as acrolein participate in many degenerative diseases. Although the nucleophilic vasodilatory drug hydralazine readily traps such species under "test-tube" conditions, whether these reactions adequately explain its efficacy in animal models of carbonyl-mediated disease is uncertain. We have previously shown that hydralazine attacks carbonyl-adducted proteins in an "adduct-trapping" reaction that appears to take precedence over direct "carbonyl-sequestering" reactions, but how this reaction conferred cytoprotection was unclear. This study explored the possibility that by increasing the bulkiness of acrolein-adducted proteins, adduct-trapping might alter the redistribution of chaperones to damaged cytoskeletal proteins that are known targets for acrolein. Using A549 lung adenocarcinoma cells, the levels of chaperones heat shock protein (Hsp) 40, Hsp70, Hsp90, and Hsp110 were measured in intermediate filament extracts prepared after a 3-h exposure to acrolein. Exposure to acrolein alone modestly increased the levels of all four chaperones. Coexposure to hydralazine (10-100 μM) strongly suppressed cell ATP loss while producing strong adduct-trapping in intermediate filaments. Most strikingly, hydralazine selectively boosted the levels of cytoskeletal-associated Hsp90, including a high-mass species that was sensitive to the Hsp90 inhibitor 17-N-allylamino-17-demethoxygeldanamycin. Biochemical fractionation of acrolein- and hydralazine-treated cells revealed that hydralazine likely promoted Hsp90 migration from cytosol into other subcellular compartments. A role for Hsp90 mobilization in cytoprotection was confirmed by the finding that brief heat shock treatment suppressed acute acrolein toxicity in A549 cells. Taken together, these findings suggest that by increasing the steric bulk of carbonyl-adducted proteins, adduct-trapping drugs trigger the intracellular mobilization of the key molecular chaperone Hsp90.

  20. Woodstoves, formaldehyde, and respiratory disease

    SciTech Connect

    Tuthill, R.W.

    1984-12-01

    Telephone interviews were completed in Western Massachusetts in April 1983 for 399 households (91.5 percent) in a random sample of households with elementary school children. Woodstoves were used in 64.7 percent of the homes, but such use was not associated with acute respiratory illness. However, formaldehyde exposure was significantly related, with a risk ratio of 2.4 (95 percent confidence interval 1.7-3.4). New construction/remodeling and new upholstered furniture had additive effects. Neither woodstove use nor formaldehyde exposure were significantly associated with asthma, chronic bronchitis, or allergies.

  1. Woodstoves, formaldehyde, and respiratory disease.

    PubMed

    Tuthill, R W

    1984-12-01

    Telephone interviews were completed in Western Massachusetts in April 1983 for 399 households (91.5 per cent) in a random sample of households with elementary school children. Woodstoves were used in 64.7 per cent of the homes, but such use was not associated with acute respiratory illness. However, formaldehyde exposure was significantly related, with a risk ratio of 2.4 (95 per cent confidence interval 1.7-3.4). New construction/remodeling and new upholstered furniture had additive effects. Neither woodstove use nor formaldehyde exposure were significantly associated with asthma, chronic bronchitis, or allergies.

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

    PubMed

    Lee, Hyun-Wook; Wang, Hsiang-Tsui; 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

    2014-06-15

    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.

  3. Formaldehyde in Insulation: Villain or Innocent Bystander?

    PubMed Central

    Lees, R. E. M.

    1983-01-01

    When urea formaldehyde foam insulation (UFFI) deteriorates, it produces an off-gas mixture whose major constituent is formaldehyde. Most investigative studies of UFFI have concentrated on formaldehyde. Health concerns fall into three groups: irritant characteristics, allergenic capabilities and potential carcinogenicity. Except for the first of these, formaldehyde's hazard potential is not clear. The extent to which formaldehyde may be responsible for UFFI's evil reputation is explored in this paper but the degree to which either substance is a real threat to health still appears to open to debate. PMID:21283296

  4. Acrolein is increased in Alzheimer's disease brain and is toxic to primary hippocampal cultures.

    PubMed

    Lovell, M A; Xie, C; Markesbery, W R

    2001-01-01

    Accumulating evidence implicates oxidative stress in the pathogenesis of several neurodegenerative diseases including Alzheimer's disease (AD). Increased lipid peroxidation, decreased levels of polyunsaturated fatty acids, and increased levels of 4-hydroxynonenal (HNE), F(2)-isoprostanes, and F(4)-neuroprostanes are present in the brain in AD. Acrolein, an alpha,beta-unsaturated aldehydic product of lipid peroxidation, is approximately 100 times more reactive than HNE and recently was demonstrated in neurofibrillary tangles in the brain in AD. In three brain regions of 10 AD patients compared with 8 age-matched control subjects, we found increased mean extractable acrolein, with the increases reaching statistical significance in the amygdala and hippocampus/parahippocampal gyrus. In hippocampal neuron cultures, acrolein was neurotoxic in a time- and concentration-dependent manner and more toxic than HNE at 5 microM concentrations of each. Acrolein exposure led to a significant concentration-dependent increase in intracellular calcium concentrations. Collectively, these data show that acrolein is increased in the brain in AD and demonstrate neurotoxicity mechanisms that might be important in the pathogenesis of neuron degeneration in AD.

  5. 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.

  6. Reductive detoxification of acrolein as a potential role for aldehyde reductase (AKR1A) in mammals.

    PubMed

    Kurahashi, Toshihiro; Kwon, Myoungsu; Homma, Takujiro; Saito, Yuka; Lee, Jaeyong; Takahashi, Motoko; Yamada, Ken-Ichi; Miyata, Satoshi; Fujii, Junichi

    2014-09-12

    Aldehyde reductase (AKR1A), a member of the aldo-keto reductase superfamily, suppresses diabetic complications via a reduction in metabolic intermediates; it also plays a role in ascorbic acid biosynthesis in mice. Because primates cannot synthesize ascorbic acid, a principle role of AKR1A appears to be the reductive detoxification of aldehydes. In this study, we isolated and immortalized mouse embryonic fibroblasts (MEFs) from wild-type (WT) and human Akr1a-transgenic (Tg) mice and used them to investigate the potential roles of AKR1A under culture conditions. Tg MEFs showed higher methylglyoxal- and acrolein-reducing activities than WT MEFs and also were more resistant to cytotoxicity. Enzymatic analyses of purified rat AKR1A showed that the efficiency of the acrolein reduction was about 20% that of glyceraldehyde. Ascorbic acid levels were quite low in the MEFs, and while the administration of ascorbic acid to the cells increased the intracellular levels of ascorbic acid, it had no affect on the resistance to acrolein. Endoplasmic reticulum stress and protein carbonylation induced by acrolein treatment were less evident in Tg MEFs than in WT MEFs. These data collectively indicate that one of the principle roles of AKR1A in primates is the reductive detoxification of aldehydes, notably acrolein, and protection from its detrimental effects.

  7. 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.

  8. 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...

  9. Acrolein induces apoptosis through the death receptor pathway in A549 lung cells: role of p53.

    PubMed

    Roy, Julie; Pallepati, Pragathi; Bettaieb, Ahmed; Averill-Bates, Diana A

    2010-03-01

    Acrolein, a highly reactive alpha,beta-unsaturated aldehyde, is an omnipresent environmental pollutant. Chronic and acute human exposures occur through exogenous and endogenous sources, including food, vapors of overheated cooking oil, house and forest fires, cigarette smoke, and automobile exhaust. Acrolein is a toxic byproduct of lipid peroxidation, which has been implicated in pulmonary, cardiac, and neurodegenerative diseases. This study shows that p53 is an initiating factor in acrolein-induced death receptor activation during apoptosis in A549 human lung cells. Exposure of cells to acrolein (0-50 micromol/L) mainly caused apoptosis, which was manifested by execution phase events such as condensation of nuclear chromatin, phosphatidylserine externalization, and poly(ADP-ribose) polymerase (PARP) cleavage. Levels of necrosis (approximately 5%) were low. Acrolein triggered the death receptor pathway of apoptosis, causing elevation of Fas ligand (FasL) and translocation of adaptor protein Fas-associated death domain to the plasma membrane. Acrolein caused activation of caspase-8, caspase-2, caspase-7, and the cross-talk pathway mediated by Bid cleavage. Activation of p53 and increased expression of p53-upregulated modulator of apoptosis (PUMA) occurred in response to acrolein. FasL upregulation and caspase-8 activation were decreased by p53 inhibitor pifithrin-alpha and antioxidant polyethylene glycol catalase. These findings increase our knowledge about the induction of cell death pathways by acrolein, which has important implications for human health.

  10. 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.

  11. Mass spectrometry-based quantification of myocardial protein adducts with acrolein in an in vivo model of oxidative stress

    PubMed Central

    Wu, Jianyong; Stevens, Jan F.; Maier, Claudia S.

    2012-01-01

    Acrolein exposure leads to the formation of protein-acrolein adducts. Protein modification by acrolein has been associated with various chronic diseases including cardiovascular and neurodegenerative diseases. Here we report an analytical strategy that enables the quantification of Michael-type protein adducts of acrolein in mitochondrial proteome samples using liquid chromatography in combination with tandem mass spectrometry and selected ion monitoring (LC-MS/MS SRM) analysis. Our approach combines site-specific identification and relative quantification at the peptide level of protein–acrolein adducts in relation to the unmodified protein thiol pool. Treatment of 3-month old rats with CCl4, an established in vivo model of acute oxidative stress, resulted in significant increases in the ratios of distinct acrolein-adducted peptides to the corresponding unmodified thiol-peptides obtained from proteins that were isolated from cardiac mitochondria. The mitochondrial proteins that were found adducted by acrolein were malate dehydrogenase, NADH dehydrogenase [ubiquinone] flavoprotein 1, cytochrome c oxidase subunit VIb isoform 1, ATP synthase d chain, and ADP/ATP translocase 1. The findings indicate that protein modification by acrolein has potential value as an index of mitochondrial oxidative stress. PMID:21809440

  12. 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...

  13. Airborne acrolein induces keratin-8 (Ser-73) hyperphosphorylation and intermediate filament ubiquitination in bronchiolar lung cell monolayers.

    PubMed

    Burcham, Philip C; Raso, Albert; Henry, Peter J

    2014-05-01

    The combustion product acrolein is a key mediator of pulmonary edema in victims of smoke inhalation injury. Since studying acrolein toxicity in conventional in vitro systems is complicated by reactivity with nucleophilic culture media constituents, we explored an exposure system which delivers airborne acrolein directly to lung cell monolayers at the air-liquid interface. Calu-3 lung adenocarcinoma cells were maintained on membrane inserts such that the basal surface was bathed in nucleophile-free media while the upper surface remained in contact with acrolein-containing air. Cells were exposed to airborne acrolein for 30 min before they were allowed to recover in fresh media, with cell sampling at defined time points to allow evaluation of toxicity and protein damage. After prior exposure to acrolein, cell ATP levels remained close to controls for 4h but decreased in an exposure-dependent manner by 24h. A loss of transepithelial electrical resistance and increased permeability to fluorescein isothiocyanate-labeled dextran preceded ATP loss. Use of antibody arrays to monitor protein expression in exposed monolayers identified strong upregulation of phospho-keratin-8 (Ser(73)) as an early consequence of acrolein exposure. These changes were accompanied by chemical damage to keratin-8 and other intermediate filament family members, while acrolein exposure also resulted in controlled ubiquitination of high mass proteins within the intermediate filament extracts. These findings confirm the usefulness of systems allowing delivery of airborne smoke constituents to lung cell monolayers during studies of the molecular basis for acute smoke intoxication injury.

  14. Reducing indoor air formaldehyde concentrations

    SciTech Connect

    Meyer, B.; Hermanns, K.

    1985-08-01

    Urea-formaldehyde resin bonded particle board, medium density fiberboard and plywood paneling are used as flooring, wall paneling, for cabinet work and in furniture, and are present in almost every office, home and public building. If large quantities of these products are used in poorly ventilated spaces, high manufacturing quality control is necessary to avoid problems of latent formaldehyde release. Indoor air formaldehyde concentrations depend on the nature of the product, the product surface to air volume (loading) factor, temperature, humidity, age and product emission rates. Standard test methods are now available for measuring product emission rates that make it possible to predict the performance of UF-bonded pressed wood materials if use conditions and environmental parameters are known. Recent modifications in adhesive and board manufacturing parameters have made it possible to reduce formaldehyde emission significantly, and UF-bonded wood products are now capable of meeting indoor air quality standard levels of 0.1 ppm under almost all customary loading conditions.

  15. Formaldehyde monitor for automobile exhausts

    NASA Technical Reports Server (NTRS)

    Easley, W. C.

    1973-01-01

    Device makes use of microwave spectral absorption in low-Q resonant Stark cell, and indications are that ultimate sensitivity of instrument is within 100 parts per billion of formaldehyde. Microwave source is very small and requires only six-volt dc bias for operation. Coarse tuning is accomplished mechanically and fine tuning by adjusting dc-bias voltage.

  16. Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Iraci, L. T.; Essin, A. M.; Golden, D. M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

  17. Report of the Federal Panel on Formaldehyde.

    PubMed Central

    1982-01-01

    The Federal Panel on Formaldehyde concluded that definitive experiments exist which demonstrate the mutagenicity and carcinogenicity of formaldehyde under laboratory conditions. Formaldehyde induces both gene mutations and chromosomal aberrations in a variety of test systems. Inhalation of formaldehyde causes cancer of the nose in rats. The concentrations of formaldehyde in inhaled air that caused nasal cancer in Fisher 344 rats are within the same order of magnitude as those to which humans may be exposed. The data presently available do not permit a direct assessment of the carcinogenicity of formaldehyde to man. Epidemiologic studies on exposed human populations are in progress and may further clarify the situation. Other experimental and human studies on toxic effects such as teratogenicity and reproductive disorders are as yet inadequate for a health risk assessment. The CIIT 24 month study on animal carcinogenicity has not yet been completely evaluated. Additional data are expected on the effects of prolonged exposure to lower doses of formaldehyde and on the possible carcinogenicity of formaldehyde in the mouse. The panel recommends that, for a comprehensive health risk assessment, further experiments be conducted on the effects of other modes of exposure (ingestion and skin penetration), the effects in humans, and on the pharmacokinetics of formaldehyde in man and animals and the possible role for formaldehyde in reproductive and chronic respiratory disorders. It is the conclusion of the panel that formaldehyde should be presumed to pose a carcinogenic risk to humans. PMID:6977445

  18. Molecular cytotoxicity mechanisms of allyl alcohol (acrolein) in budding yeast.

    PubMed

    Golla, Upendarrao; Bandi, Goutham; Tomar, Raghuvir S

    2015-06-15

    Allyl alcohol (AA) is one of the environmental pollutants used as a herbicide and industrial chemical. AA undergoes enzymatic oxidation in vivo to form Acrolein (Acr), a highly reactive and ubiquitous environmental toxicant. The exposure to AA/Acr has detrimental effects on cells and is highly fatal. In corroboration to the current literature describing AA/Acr toxicity, this study aimed to investigate the molecular cytotoxicity mechanisms of AA/Acr using budding yeast as a eukaryotic model organism. Genome-wide transcriptome analysis of cells treated with a sublethal dose of AA (0.4 mM) showed differential regulation of approximately 30% of the yeast genome. Functional enrichment analysis of the AA transcriptome revealed that genes belong to diverse cellular processes including the cell cycle, DNA damage repair, metal homeostasis, stress response genes, ribosomal biogenesis, metabolism, meiosis, ubiquitination, cell morphogenesis, and transport. Moreover, we have identified novel molecular targets of AA/Acr through genetic screening, which belongs to oxidative stress, DNA damage repair, iron homeostasis, and cell wall integrity. This study also demonstrated the epigenetic basis of AA/Acr toxicity mediated through histone tails and chromatin modifiers. Interestingly, our study disclosed the use of pyrazole and ethanol as probable antidotes for AA intoxication. For the first time, this study also demonstrated the reproductive toxicity of AA/Acr using the yeast gametogenesis (spermatogenesis) model. Altogether, this study unravels the molecular mechanisms of AA/Acr cytotoxicity and facilitates the prediction of biomarkers for toxicity assessment and therapeutic approaches. PMID:25919230

  19. Enhancement of the acrolein-induced production of reactive oxygen species and lung injury by GADD34.

    PubMed

    Sun, Yang; Ito, Sachiko; Nishio, Naomi; Tanaka, Yuriko; Chen, Nana; Liu, Lintao; Isobe, Ken-ichi

    2015-01-01

    Chronic obstructive pulmonary disease (COPD) is characterized by lung destruction and inflammation. As a major compound of cigarette smoke, acrolein plays a critical role in the induction of respiratory diseases. GADD34 is known as a growth arrest and DNA damage-related gene, which can be overexpressed in adverse environmental conditions. Here we investigated the effects of GADD34 on acrolein-induced lung injury. The intranasal exposure of acrolein induced the expression of GADD34, developing the pulmonary damage with inflammation and increase of reactive oxygen species (ROS). Conversely, the integrality of pulmonary structure was preserved and the generation of ROS was reduced in GADD34-knockout mice. Acrolein-induced phosphorylation of eIF2α in GADD34-knockout epithelial cells by shRNA protected cell death by reducing misfolded protein-caused oxidative stress. These data indicate that GADD34 participates in the development of acrolein-induced lung injury.

  20. 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

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

    PubMed

    Dostert, Karl-Heinz; O'Brien, Casey P; Ivars-Barceló, Francisco; Schauermann, Swetlana; Freund, Hans-Joachim

    2015-10-28

    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

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

    PubMed Central

    Deng, Yu-Hui; Cui, Fa-Cai

    2016-01-01

    Introduction 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). Material and methods 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. Results 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). Conclusions 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. PMID:27478470

  3. A new airborne formaldehyde instrument: Compact Formaldehyde Fluorescence Experiment (COFFEE)

    NASA Astrophysics Data System (ADS)

    Hanisco, T. F.; Bailey, S. A.; Swanson, A. K.; Wolfe, G. M., Jr.

    2014-12-01

    We present the operating principles of a new instrument designed for operation on small aircraft. The instrument uses a new non-resonant fluorescence technique to take advantage of compact industrial lasers to make a small, robust package that can measure formaldehyde at sensitivities better than 100 ppt in 1 second integration. The instrument is designed to fly on the Alphajet at NASA Ames but can be modified to fly on other small aircraft.

  4. Upregulation of endothelial heme oxygenase-1 expression through the activation of the JNK pathway by sublethal concentrations of acrolein

    SciTech Connect

    Wu, C.C.; Hsieh, C.W.; Lai, P.H.; Lin, J.B.; Liu, Y.C.; Wung, B.S. . E-mail: bswung@mail.ncyu.edu.tw

    2006-08-01

    Acrolein is a highly electrophilic {alpha},{beta}-unsaturated aldehyde that is present in cigarette smoke. Heme oxygenase-1 (HO-1) is a cytoprotective enzyme activated by various such electrophilic compounds. In this study, the regulatory effects of acrolein upon the expression of HO-1 were investigated in endothelial cells (ECs). We demonstrate that acrolein induces the elevation of HO-1 protein levels, and subsequent enzyme activity, at non-cytotoxic concentrations. An additional {alpha},{beta}-unsaturated aldehyde, cinnamaldehyde, was also found to increase HO-1 expression and have less cytotoxicity than acrolein. Moreover, acrolein-mediated HO-1 induction is abrogated in the presence of actinomycin D and cycloheximide. Nrf2 is a transcription factor involved in the induction of HO-1 through an antioxidant response element (ARE) in the promoter region of the HO-1 gene. We show that acrolein induces Nrf2 translocation and ARE-luciferase reporter activity. Acrolein was also found to induce the production of both superoxide and H{sub 2}O{sub 2} at levels greater than 100 {mu}M. However, with the exception of NAC, no antioxidant generated any effect upon acrolein-dependent HO-1 expression in ECs. Our present findings suggest that reactive oxygen species (ROS) may not be a major modulator for HO-1 induction. Using buthionine sulfoximine to deplete the intracellular GSH levels further enhanced the effects of acrolein. We also found that cellular GSH level was rapidly reduced after both 10 and 100 {mu}M acrolein treatment. However, after 6 h of exposure to ECs, only 10 {mu}M acrolein treatment increases GSH level. In addition, only the JNK inhibitor SP600125 and tyrosine kinase inhibitor genistein had any significant inhibitory impact upon the upregulation of HO-1 by acrolein. Pretreatment with a range of other PI3 kinase inhibitors, including wortmannin and LY294002, showed no effects. Hence, we show in our current experiments that a sublethal concentration of

  5. Reaction mechanism for methanol oxidation on Au(1 1 1): A density functional theory study

    NASA Astrophysics Data System (ADS)

    Liu, Shuping; Jin, Peng; Zhang, Donghui; Hao, Ce; Yang, Xueming

    2013-01-01

    The microscopic reaction mechanism for methanol oxidation on Au(1 1 1) surface has been thoroughly investigated by means of density functional theory (DFT) computations. The adsorption geometries and energies were obtained for all the adsorbates, including the reactants, the products, and various possible intermediates on the metal. According to different oxygen conditions, we propose two possible reaction pathways for methanol oxidation on Au(1 1 1): (1) HCHO esterification: the intermediate formaldehyde and methoxy couple to yield methyl formate at low oxygen coverage or without the presence of oxygen atoms; (2) HCHO oxidation: the formaldehyde is oxidized to form formate at high oxygen coverage, which further dissociates to give CO2. Our study emphasizes the critical role of oxygen coverage during the methanol oxidation reaction, and can perfectly explain the difference in product distributions observed in previous experiments.

  6. Imaging sequential dehydrogenation of methanol on Cu(110) with a scanning tunneling microscope

    NASA Astrophysics Data System (ADS)

    Kitaguchi, Y.; Shiotari, A.; Okuyama, H.; Hatta, S.; Aruga, T.

    2011-05-01

    Adsorption of methanol and its dehydrogenation on Cu(110) were studied by using a scanning tunneling microscope (STM). Upon adsorption at 12 K, methanol preferentially forms clusters on the surface. The STM could induce dehydrogenation of methanol sequentially to methoxy and formaldehyde. This enabled us to study the binding structures of these products in a single-molecule limit. Methoxy was imaged as a pair of protrusion and depression along the [001] direction. This feature is fully consistent with the previous result that it adsorbs on the short-bridge site with the C-O axis tilted along the [001] direction. The axis was induced to flip back and forth by vibrational excitations with the STM. Two configurations were observed for formaldehyde, whose structures were proposed based on their characteristic images and motions.

  7. Collisional excitation of interstellar formaldehyde

    NASA Technical Reports Server (NTRS)

    Green, S.; Garrison, B. J.; Lester, W. A., Jr.; Miller, W. H.

    1978-01-01

    Previous calculations for rates of excitation of ortho-H2CO by collisions with He have been extended to higher rotational levels and kinetic temperatures to 80 K. Rates for para-H2CO have also been computed. Pressure-broadening widths for several spectral lines have been obtained from these calculations and are found to agree with recent data within the experimental uncertainty of 10%. Excitation of formaldehyde by collisions with H2 molecules is also discussed.

  8. Protection of HepG2 cells against acrolein toxicity by 2-cyano-3,12-dioxooleana-1,9-dien-28-imidazolide via glutathione-mediated mechanism

    PubMed Central

    Shah, Halley; Speen, Adam M; Saunders, Christina; Brooke, Elizabeth AS; Nallasamy, Palanisamy; Zhu, Hong

    2015-01-01

    Acrolein is an environmental toxicant, mainly found in smoke released from incomplete combustion of organic matter. Several studies showed that exposure to acrolein can lead to liver damage. The mechanisms involved in acrolein-induced hepatocellular toxicity, however, are not completely understood. This study examined the cytotoxic mechanisms of acrolein on HepG2 cells. Acrolein at pathophysiological concentrations was shown to cause apoptotic cell death and an increase in levels of protein carbonyl and thiobarbituric acid reactive acid substances. Acrolein also rapidly depleted intracellular glutathione (GSH), GSH-linked glutathione-S-transferases, and aldose reductase, three critical cellular defenses that detoxify reactive aldehydes. Results further showed that depletion of cellular GSH by acrolein preceded the loss of cell viability. To further determine the role of cellular GSH in acrolein-mediated cytotoxicity, buthionine sulfoximine (BSO) was used to inhibit cellular GSH biosynthesis. It was observed that depletion of cellular GSH by BSO led to a marked potentiation of acrolein-mediated cytotoxicity in HepG2 cells. To further assess the contribution of these events to acrolein-induced cytotoxicity, triterpenoid compound 2-cyano-3,12-dioxooleana-1,9-dien-28-imidazolide (CDDO-Im) was used for induction of GSH. Induction of GSH by CDDO-Im afforded cytoprotection against acrolein toxicity in HepG2 cells. Furthermore, BSO significantly inhibited CDDO-Im-mediated induction in cellular GSH levels and also reversed cytoprotective effects of CDDO-Im in HepG2 cells. These results suggest that GSH is a predominant mechanism underlying acrolein-induced cytotoxicity as well as CDDO-Im-mediated cytoprotection. This study may provide understanding on the molecular action of acrolein which may be important to develop novel strategies for the prevention of acrolein-mediated toxicity. PMID:25504014

  9. Protection of HepG2 cells against acrolein toxicity by 2-cyano-3,12-dioxooleana-1,9-dien-28-imidazolide via glutathione-mediated mechanism.

    PubMed

    Shah, Halley; Speen, Adam M; Saunders, Christina; Brooke, Elizabeth A S; Nallasamy, Palanisamy; Zhu, Hong; Li, Y Robert; Jia, Zhenquan

    2015-10-01

    Acrolein is an environmental toxicant, mainly found in smoke released from incomplete combustion of organic matter. Several studies showed that exposure to acrolein can lead to liver damage. The mechanisms involved in acrolein-induced hepatocellular toxicity, however, are not completely understood. This study examined the cytotoxic mechanisms of acrolein on HepG2 cells. Acrolein at pathophysiological concentrations was shown to cause apoptotic cell death and an increase in levels of protein carbonyl and thiobarbituric acid reactive acid substances. Acrolein also rapidly depleted intracellular glutathione (GSH), GSH-linked glutathione-S-transferases, and aldose reductase, three critical cellular defenses that detoxify reactive aldehydes. Results further showed that depletion of cellular GSH by acrolein preceded the loss of cell viability. To further determine the role of cellular GSH in acrolein-mediated cytotoxicity, buthionine sulfoximine (BSO) was used to inhibit cellular GSH biosynthesis. It was observed that depletion of cellular GSH by BSO led to a marked potentiation of acrolein-mediated cytotoxicity in HepG2 cells. To further assess the contribution of these events to acrolein-induced cytotoxicity, triterpenoid compound 2-cyano-3,12-dioxooleana-1,9-dien-28-imidazolide (CDDO-Im) was used for induction of GSH. Induction of GSH by CDDO-Im afforded cytoprotection against acrolein toxicity in HepG2 cells. Furthermore, BSO significantly inhibited CDDO-Im-mediated induction in cellular GSH levels and also reversed cytoprotective effects of CDDO-Im in HepG2 cells. These results suggest that GSH is a predominant mechanism underlying acrolein-induced cytotoxicity as well as CDDO-Im-mediated cytoprotection. This study may provide understanding on the molecular action of acrolein which may be important to develop novel strategies for the prevention of acrolein-mediated toxicity.

  10. Imino [4+4] cycloaddition products as exclusive and biologically relevant acrolein-amine conjugates are intermediates of 3-formyl-3,4-dehydropiperidine (FDP), an acrolein biomarker.

    PubMed

    Takamatsu, Masayuki; Fukase, Koichi; Kurbangalieva, Almira; Tanaka, Katsunori

    2014-11-15

    We demonstrated synthetically that the eight-membered heterocycles 2,6,9-triazabicyclo[3.3.1]nonanes and 1,5-diazacyclooctanes are the initial and exclusive products of the reaction, through an imino [4+4] cycloaddition, of biologically relevant amines with acrolein. The stabilities of the aminoacetals within the eight-membered heterocycles determined whether the product was subsequently transformed gradually into the 3-formyl-3,4-dehydropiperidine (FDP), which is widely used as an oxidative stress marker. The reactivity profiles discovered in this study suggested that some of the imino [4+4] cycloaddition products are reactive intermediates of FDP and contribute to the mechanisms underlying the oxidative stress response to acrolein.

  11. The Methanol Economy Project

    SciTech Connect

    Olah, George; Prakash, G. K.

    2014-02-01

    The Methanol Economy Project is based on the concept of replacing fossil fuels with methanol generated either from renewable resources or abundant natural (shale) gas. The full methanol cycle was investigated in this project, from production of methanol through bromination of methane, bireforming of methane to syngas, CO2 capture using supported amines, co-electrolysis of CO2 and water to formate and syngas, decomposition of formate to CO2 and H2, and use of formic acid in a direct formic acid fuel cell. Each of these projects achieved milestones and provided new insights into their respective fields.

  12. Acrolein activates cell survival and apoptotic death responses involving the endoplasmic reticulum in A549 lung cells.

    PubMed

    Tanel, André; Pallepati, Pragathi; Bettaieb, Ahmed; Morin, Patrick; Averill-Bates, Diana A

    2014-05-01

    Acrolein, a highly reactive α,β-unsaturated aldehyde, is a product of endogenous lipid peroxidation. It is a ubiquitous environmental pollutant that is generated mainly by smoke, overheated cooking oil and vehicle exhaust. Acrolein damages cellular proteins, which could lead to accumulation of aberrantly-folded proteins in the endoplasmic reticulum (ER). This study determines the mechanisms involved in acrolein-induced apoptosis mediated by the ER and possible links with the ER stress response in human A549 lung cells. The exposure of cells to acrolein (15-50μM) for shorter times of 15 to 30min activated several ER stress markers. These included the ER chaperone protein BiP and the three ER sensors: (i) the survival/rescue molecules protein kinase RNA (PKR)-like ER kinase (PERK) and eukaryotic initiation factor 2 alpha (eIF2α) were phosphorylated; (ii) cleavage of activating transcription factor 6 (ATF6) occurred, and (iii) inositol-requiring protein-1 alpha (IRE1α) was phosphorylated. Acrolein (25-50μM) caused apoptotic cell death mediated by the ER after 2h, which was characterised by the induction of CHOP and activation of ER proteases calpain and caspase-4. Calpain and caspase-7 were the initiating factors for caspase-4 activation in acrolein-induced apoptosis. These results increase our knowledge about cellular responses to acrolein in lung cells, which have implications for human health.

  13. Microencapsulated fragrances in melamine formaldehyde resins.

    PubMed

    Bône, Stéphane; Vautrin, Claire; Barbesant, Virginie; Truchon, Stéphane; Harrison, Ian; Geffroy, Cédric

    2011-01-01

    The process for making melamine formaldehyde microcapsules containing fragrant oil is well-known. Recently, this technology has been used to enhance the olfactory performance on fabrics. However keeping the fragrance in the capsule during storage, improving the olfactory benefit and releasing a low amount of formaldehyde is highly challenging. To answer these challenges, Givaudan has developed its own melamine formaldehyde microcapsule, called Mechacaps, which is described in this article.

  14. Gaseous reference standards of formaldehyde from trioxane.

    PubMed

    Brewer, Paul J; di Meane, Elena Amico; Vargha, Gergely M; Brown, Richard J C; Milton, Martin J T

    2013-04-15

    We have developed a dynamic reference standard of gaseous formaldehyde based on diffusion of the sublimate of trioxane and thermal conversion to formaldehyde in the gas phase. We have also produced a gravimetric standard for formaldehyde in a nitrogen matrix, also by thermal conversion of the sublimate of trioxane. Analysis of the gravimetric standard with respect to the dynamic standard has confirmed the comparability of the static and dynamic gravimetric values.

  15. Mitigation of sensory and motor deficits by acrolein scavenger phenelzine in a rat model of spinal cord contusive injury.

    PubMed

    Chen, Zhe; Park, Jonghyuck; Butler, Breanne; Acosta, Glen; Vega-Alvarez, Sasha; Zheng, Lingxing; Tang, Jonathan; McCain, Robyn; Zhang, Wenpeng; Ouyang, Zheng; Cao, Peng; Shi, Riyi

    2016-07-01

    Currently there are no effective therapies available for the excruciating neuropathic pain that develops after spinal cord injuries (SCI). As such, a great deal of effort is being put into the investigation of novel therapeutic targets that can alleviate this pain. One such target is acrolein, a highly reactive aldehyde produced as a byproduct of oxidative stress and inflammation that is capable of activating the transient receptor potential ankyrin 1 (TRPA1) cation channel, known to be involved in the transmission and propagation of chronic neuropathic pain. One anti-acrolein agent, hydralazine, has already been shown to reduce neuropathic pain behaviors and offer neuroprotection after SCI. This study investigates another acrolein scavenger, phenelzine, for its possible role of alleviating sensory hypersensitivity through acrolein suppression. The results show that phenelzine is indeed capable of attenuating neuropathic pain behaviors in acute, delayed, and chronic administration schedules after injury in a rat model of SCI. In addition, upon the comparison of hydralazine to phenelzine, both acrolein scavengers displayed a dose-dependent response in the reduction of acrolein in vivo. Finally, phenelzine proved capable of providing locomotor function recovery and neuroprotection of spinal cord tissue when administered immediately after injury for 2 weeks. These results indicate that phenelzine may be an effective treatment for neuropathic pain after SCI and likely a viable alternative to hydralazine. We have shown that phenelzine can attenuate neuropathic pain behavior in acute, delayed, and chronic administration in post-SCI rats. This was accompanied by a dose-dependent reduction in an acrolein metabolite in urine and an acrolein adduct in spinal cord tissue, and the suppression of TRPA1 over-expression in central and peripheral locations post-trauma. Acrolein scavenging might be a novel therapeutic strategy to reduce post-SCI neuropathic pain.

  16. Studies on the toxicity of acetone, acrolein and carbon dioxide on stored-product insects and wheat seed.

    PubMed

    Pourmirza, Ali Asghar; Tajbakhsh, Mehdie

    2008-04-01

    In laboratory experiments toxicity of acetone, acrolein and carbon dioxide were investigated against 4 species of stored-product insects. In all experiments, acrolein was the most toxic compound to the tested insects. In empty-space trials, estimated LD50 values of acrolein for adults of Tribolium castaneum (Herbst) (Tenebrionidae), Rhizopertha dominica (F.) (Bostrychidae), Sitophilus oryzae L. (Curculionidae) and Oryzaephilus surinamensis L. (Silvanidae) were 7.26, 6.09, 6.37 and 5.65 microl L(-1), respectively. Penetration tests revealed that acetone and acrolein vapors could penetrate into the wheat mass and kill concealed insects in interkernel spaces. Comparison of LD50 values of acrolein between empty-space tests and penetration experiments indicated that the increase in penetration toxicity was 4.96, 4.54, 3.64 and 3.43-fold for T. castaneum, R. dominica, S. oryzae and O. surinamensis, respectively. The effect of carbon dioxide on the toxicity of acrolein and acetone was synergistic. In the hidden infestation trials, the acrolein vapors destroyed the developmental stages of S. oryzae concealed inside the wheat kernels and resulted in a complete control with concentration of 80 microl L(-1) for 24 h and subsequently observed during 8 weeks after the exposure. Wheat germination and plumule length was reduced following exposure to all doses of acrolein. Acetone and carbon dioxide were harmless to wheat seed viability. The mixture of carbon dioxide with acrolein can be considered as a potential fumigant for replacing methyl bromide or phosphine under ambient storage conditions specifically in empty-space fumigations.

  17. Mitigation of sensory and motor deficits by acrolein scavenger phenelzine in a rat model of spinal cord contusive injury.

    PubMed

    Chen, Zhe; Park, Jonghyuck; Butler, Breanne; Acosta, Glen; Vega-Alvarez, Sasha; Zheng, Lingxing; Tang, Jonathan; McCain, Robyn; Zhang, Wenpeng; Ouyang, Zheng; Cao, Peng; Shi, Riyi

    2016-07-01

    Currently there are no effective therapies available for the excruciating neuropathic pain that develops after spinal cord injuries (SCI). As such, a great deal of effort is being put into the investigation of novel therapeutic targets that can alleviate this pain. One such target is acrolein, a highly reactive aldehyde produced as a byproduct of oxidative stress and inflammation that is capable of activating the transient receptor potential ankyrin 1 (TRPA1) cation channel, known to be involved in the transmission and propagation of chronic neuropathic pain. One anti-acrolein agent, hydralazine, has already been shown to reduce neuropathic pain behaviors and offer neuroprotection after SCI. This study investigates another acrolein scavenger, phenelzine, for its possible role of alleviating sensory hypersensitivity through acrolein suppression. The results show that phenelzine is indeed capable of attenuating neuropathic pain behaviors in acute, delayed, and chronic administration schedules after injury in a rat model of SCI. In addition, upon the comparison of hydralazine to phenelzine, both acrolein scavengers displayed a dose-dependent response in the reduction of acrolein in vivo. Finally, phenelzine proved capable of providing locomotor function recovery and neuroprotection of spinal cord tissue when administered immediately after injury for 2 weeks. These results indicate that phenelzine may be an effective treatment for neuropathic pain after SCI and likely a viable alternative to hydralazine. We have shown that phenelzine can attenuate neuropathic pain behavior in acute, delayed, and chronic administration in post-SCI rats. This was accompanied by a dose-dependent reduction in an acrolein metabolite in urine and an acrolein adduct in spinal cord tissue, and the suppression of TRPA1 over-expression in central and peripheral locations post-trauma. Acrolein scavenging might be a novel therapeutic strategy to reduce post-SCI neuropathic pain. PMID:27060873

  18. Laboratory evaluation of an aldehyde scrubber system specifically for the detection of acrolein.

    PubMed

    Knighton, W Berk; Herndon, Scott C; Shorter, Joanne H; Miake-Lye, Richard C; Zahniser, Mark S; Akiyama, Kenichi; Shimono, Akio; Kitasaka, Kazuya; Shimajiri, Hatsumi; Sugihara, Koichi

    2007-11-01

    We demonstrate the use of an aldehyde scrubber system to resolve isobaric aldehyde/alkene interferences in a proton transfer reaction mass spectrometer (PTR-MS) by selectively removing the aldehydes from the gas mixture without loss of quantitative information for the alkene components. The aldehyde scrubber system uses a bisulfite solution, which scrubs carbonyl compounds from the gas stream by forming water-soluble carbonyl bisulfite addition products, and has been evaluated using a synthetic mixture of acrolein and isoprene. Trapping efficiencies of acrolein exceeded 97%, whereas the transmission efficiency of isoprene was better than 92%. Quantification of the PTR-MS response to acrolein was validated through an intercomparison study that included two derivatization methods, dinitrophenylhydrazine (DNPH) and O-(4-cyano-2-ethoxybenzyl)hydroxylamine (CNET), and a spectroscopic method using a quantum cascade laser infrared absorption spectroscopy (QCL) instrument. Finally, using cigarette smoke as a complex matrix, the acrolein content was assessed using the scrubber and compared with direct QCL-based detection. PMID:18069460

  19. Molecular mechanisms of acrolein-mediated myelin destruction in CNS trauma and disease.

    PubMed

    Shi, R; Page, J C; Tully, M

    2015-01-01

    Myelin is a critical component of the nervous system facilitating efficient propagation of electrical signals and thus communication between the central and peripheral nervous systems and the organ systems that they innervate throughout the body. In instances of neurotrauma and neurodegenerative disease, injury to myelin is a prominent pathological feature responsible for conduction deficits, and leaves axons vulnerable to damage from noxious compounds. Although the pathological mechanisms underlying myelin loss have yet to be fully characterized, oxidative stress (OS) appears to play a prominent role. Specifically, acrolein, a neurotoxic aldehyde that is both a product and an instigator of OS, has been observed in studies to elicit demyelination through calcium-independent and -dependent mechanisms and also by affecting glutamate uptake and promoting excitotoxicity. Furthermore, pharmacological scavenging of acrolein has demonstrated a neuroprotective effect in animal disease models, by conserving myelin's structural integrity and alleviating functional deficits. This evidence indicates that acrolein may be a key culprit of myelin damage while acrolein scavenging could potentially be a promising therapeutic approach for patients suffering from nervous system trauma and disease.

  20. Iron-tellurium-selenium mixed oxide catalysts for the selective oxidation of propylene to acrolein

    SciTech Connect

    Patel, B.M.; Price, G.L. )

    1990-05-01

    This paper reports on iron-tellurium-selenium mixed oxide catalysts prepared by coprecipitation from aqueous solution investigated for the propylene to acrolein reaction in the temperature range 543-773 K. Infrared spectroscopy, electron dispersive X-ray analysis, X-ray diffraction, and isotopic tracer techniques have also been employed to characterize this catalytic system. Properties of the Fe-Te-Se mixed oxide catalysts have been compared with Fe-Te mixed oxides in an effort to deduce the functionality of Se. The selenium in the Fe-Te-Se-O catalyst has been found to be the hydrocarbon activating site. The activation energies for the acrolein and carbon dioxide formation are 71 and 54 kJ/mol, respectively. Reactions carried out with {sup 18}O{sub 2} have shown lattice oxygen to be primarily responsible for the formation of both acrolein and carbon dioxide. The initial and rate-determining step for acrolein formation is hydrogen abstraction as determined by an isotope effect associated with the C{sub 3}D{sub 6} reaction. No isotope effect is observed for carbon dioxide formation from C{sub 3}D{sub 6} suggesting that CO{sub 2} is formed by parallel, not consecutive, oxidation of propylene.

  1. One-pot sequential asymmetric hydrogenation of β-aryl-β-aryloxy acroleins.

    PubMed

    Liu, Yufeng; Chen, Jianzhong; Zhang, Zhenfeng; Qin, Jian; Zhao, Min; Zhang, Wanbin

    2016-08-01

    A one-pot sequential asymmetric hydrogenation of β-aryl-β-aryloxy acroleins has been realized for the preparation of chiral 3-aryl-3-aryloxy alcohols with excellent yields and good enantioselectivities. This methodology can be employed in new synthetic routes for the synthesis of fluoxetine, atomoxetine, and related analogues. PMID:27439010

  2. Acrolein contributes to TRPA1 up-regulation in peripheral and central sensory hypersensitivity following spinal cord injury.

    PubMed

    Park, Jonghyuck; Zheng, Lingxing; Acosta, Glen; Vega-Alvarez, Sasha; Chen, Zhe; Muratori, Breanne; Cao, Peng; Shi, Riyi

    2015-12-01

    Acrolein, an endogenous aldehyde, has been shown to be involved in sensory hypersensitivity after rat spinal cord injury (SCI), for which the pathogenesis is unclear. Acrolein can directly activate a pro-algesic transient receptor protein ankyrin 1 (TRPA1) channel that exists in sensory neurons. Both acrolein and TRPA1 mRNA are elevated post SCI, which contributes to the activation of TRPA1 by acrolein and consequently, neuropathic pain. In the current study, we further showed that, post-SCI elevation of TRPA1 mRNA exists not only in dorsal root ganglias but also in both peripheral (paw skin) and central endings of primary afferent nerves (dorsal horn of spinal cord). This is the first indication that pain signaling can be over-amplified in the peripheral skin by elevated expressions of TRPA1 following SCI, in addition over-amplification previously seen in the spinal cord and dorsal root ganglia. Furthermore, we show that acrolein alone, in the absence of physical trauma, could lead to the elevation of TRPA1 mRNA at various locations when injected to the spinal cord. In addition, post-SCI elevation of TRPA1 mRNA could be mitigated using acrolein scavengers. Both of these attributes support the critical role of acrolein in elevating TRPA1 expression through gene regulation. Taken together, these data indicate that acrolein is likely a critical causal factor in heightening pain sensation post-SCI, through both the direct binding of TRPA1 receptor, and also by boosting the expression of TRPA1. Finally, our data also further support the notion that acrolein scavenging may be an effective therapeutic approach to alleviate neuropathic pain after SCI. We propose that the trauma-mediated elevation of acrolein causes neuropathic pain through at least two mechanisms: acrolein stimulates the production of transient receptor protein ankyrin 1 (TRPA1) in both central and peripheral locations, and it activates TRPA1 channels directly. Therefore, acrolein appears to be a critical

  3. Formaldehyde: a comparative evaluation of four monitoring methods

    SciTech Connect

    Coyne, L.B.; Cook, R.E.; Mann, J.R.; Bouyoucos, S.; McDonald, O.F.; Baldwin, C.L.

    1985-10-01

    The performances of four formaldehyde monitoring devices were compared in a series of laboratory and field experiments. The devices evaluated included the DuPont C-60 formaldehyde badge, the SKC impregnated charcoal tube, an impinger/polarographic method and the MDA Lion formaldemeter. The major evaluation parameters included: concentration range, effects of humidity, sample storage, air velocity, accuracy, precision, interferences from methanol, styrene, 1,3-butadiene, sulfur dioxide and dimethylamine. Based on favorable performances in the laboratory and field, each device was useful for monitoring formaldehyde in the industrial work environment; however, these devices were not evaluated for residential exposure assessment. The impinger/polarographic method had a sensitivity of 0.06 ppm, based on a 20-liter air sample volume, and accurately determined the short-term excursion limit (STEL). It was useful for area monitoring but was not very practical for time-weighted average (TWA) personal monitoring measurements. The DuPont badge had a sensitivity of 2.8 ppm-hr and accurately and simply determined TWA exposures. It was not sensitive enough to measure STEL exposures, however, and positive interferences resulted if 1,3-butadiene was present. The SKC impregnated charcoal tube measured both TWA and STEL concentrations and had a sensitivity of 0.06 ppm based on a 25-liter air sample volume. Lightweight and simple to use, the MDA Lion formaldemeter had a sensitivity of 0.2 ppm. It had the advantage of giving an instantaneous reading in the field; however, it must be used with caution because it responded to many interferences. The method of choice depended on the type of sampling required, field conditions encountered during sampling and an understanding of the limitations of each monitoring device.

  4. Formaldehyde-releasers in cosmetics: relationship to formaldehyde contact allergy. Part 2. Patch test relationship to formaldehyde contact allergy, experimental provocation tests, amount of formaldehyde released, and assessment of risk to consumers allergic to formaldehyde.

    PubMed

    de Groot, Anton; White, Ian R; Flyvholm, Mari-Ann; Lensen, Gerda; Coenraads, Pieter-Jan

    2010-01-01

    This is the second part of an article on formaldehyde-releasers in cosmetics. The patch test relationship between the releasers in cosmetics to formaldehyde contact allergy is reviewed and it is assessed whether products preserved with formaldehyde-releasers may contain enough free formaldehyde to pose a threat to individuals with contact allergy to formaldehyde. There is a clear relationship between positive patch test reactions to formaldehyde-releasers and formaldehyde contact allergy: 15% of all reactions to 2-bromo-2-nitropropane-1,3-diol and 40-60% of the reactions to the other releasers are caused by a reaction to the formaldehyde in the test material. There is only fragmented data on the amount of free formaldehyde in cosmetics preserved with formaldehyde donors. However, all releasers (with the exception of 2-bromo-2-nitropropane-1,3-diol, for which adequate data are lacking) can, in the right circumstances of concentration and product composition, release >200 p.p.m. formaldehyde, which may result in allergic contact dermatitis. Whether this is actually the case in any particular product cannot be determined from the ingredient labelling. Therefore, we recommend advising patients allergic to formaldehyde to avoid leave-on cosmetics preserved with quaternium-15, diazolidinyl urea, DMDM hydantoin, or imidazolidinyl urea, acknowledging that many would tolerate some products. PMID:20136876

  5. Formaldehyde-releasers: relationship to formaldehyde contact allergy. Part 2. Formaldehyde-releasers in clothes: durable press chemical finishes.

    PubMed

    de Groot, Anton C; Le Coz, Christophe J; Lensen, Gerda J; Flyvholm, Mari-Ann; Maibach, Howard I; Coenraads, Pieter-Jan

    2010-07-01

    This is the second part of a review article on formaldehyde-releasers used as durable press chemical finishes (DPCF) in textiles. The early finishes contained large amounts of free formaldehyde, which led to many cases of allergic contact dermatitis to clothes in the 1950s and 1960s. Currently, most finishes are based on modified dimethylol dihydroxyethyleneurea, which releases less formaldehyde. Nevertheless, recent studies in the United States and Israel have identified patients reacting to DPCF, considered to have allergic contact reactions to clothes, either from formaldehyde released by the DPCF therein or from the DPCF per se (in patients negative to formaldehyde). However, all studies had some weaknesses in design or interpretation and in not a single case has the clinical relevance been proven. The amount of free formaldehyde in most garments will likely be below the threshold for the elicitation of dermatitis for all but the most sensitive patients. The amount of free cyclized urea DPCF in clothes is unlikely to be high enough to cause sensitization. Patch test reactions to formaldehyde-releasing DPCF will in most cases represent a reaction to formaldehyde released from the test material.

  6. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, S.; Kumar, R.; Krumpelt, M.

    1999-08-17

    A partial oxidation reformer is described comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell. 7 figs.

  7. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    1999-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  8. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    2001-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  9. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, S.; Kumar, R.; Krumpelt, M.

    1999-08-24

    A partial oxidation reformer is described comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell. 7 figs.

  10. Measurement of formaldehyde concentrations in a subatmospheric steam-formaldehyde autoclave.

    PubMed Central

    Marcos, D; Wiseman, D

    1979-01-01

    A method has been developed for measuring formaldehyde concentrations in a subatmospheric steam-formaldehyde autoclave. Data obtained using this method indicate that the concentration of formaldehyde in the chamber atmosphere is not homogeneous and that it decreases rapidly with time. The penetration of formaldehyde vapour into narrow tubes has also been investigated and was shown to be dependent on the length-to-bore ratio of the tubes. The formaldehyde concentration within the tubes could be increased by using a lower vacuum in the air removal stage at the beginning of the cycle. PMID:572833

  11. Role of by-products of lipid oxidation in Alzheimer's disease brain: a focus on acrolein.

    PubMed

    Singh, Manjeet; Dang, Thanh Nam; Arseneault, Madeleine; Ramassamy, Charles

    2010-01-01

    Abundant data consistently support the idea that oxidative stress occurs and is a constant feature of Alzheimer's disease (AD). Some recent evidence indicated that phenomenon is an early event and might be implicated in the pathogenesis of this disease. Lipid peroxidation leads to the formation of a number of aldehydes by-products, including malondialdehyde (MDA), 4-hydroxy-2-nonenal (HNE), and acrolein. The most abundant aldehydes are HNE and MDA while acrolein is the most reactive. Increased levels of specific HNE-histidine and glutathione-HNE Michael adducts in AD brain has been reported. Proteomic analysis demonstrated a large number of protein-bound HNE in AD brain. F2-isoprostanes (F2-IsoPs) levels and neuroprostanes were also significantly increased in mild cognitive impairment (MCI) patients and in late-stage AD. In brain from patients with AD, acrolein has been found to be elevated in hippocampus and temporal cortex where oxidative stress is high. Due to its high reactivity, acrolein is not only a marker of lipid peroxidation but also an initiator of oxidative stress by adducting cellular nucleophilic groups found on proteins, lipids, and nucleic acids. Interestingly, data indicates that lipid peroxidation occurs in the brain of MCI and also in preclinical AD patients suggesting that oxidative damage may play an early role in the pathogenesis of AD. In this review, we will summarize some mechanisms implicated in the toxicity of by-products of lipid peroxidation such as IsoPs, HNE, and acrolein and their implication in AD.

  12. Translesion synthesis past acrolein-derived DNA adducts by human mitochondrial DNA polymerase γ.

    PubMed

    Kasiviswanathan, Rajesh; Minko, Irina G; Lloyd, R Stephen; Copeland, William C

    2013-05-17

    Acrolein, a mutagenic aldehyde, is produced endogenously by lipid peroxidation and exogenously by combustion of organic materials, including tobacco products. Acrolein reacts with DNA bases forming exocyclic DNA adducts, such as γ-hydroxy-1,N(2)-propano-2'-deoxyguanosine (γ-HOPdG) and γ-hydroxy-1,N(6)-propano-2'-deoxyadenosine (γ-HOPdA). The bulky γ-HOPdG adduct blocks DNA synthesis by replicative polymerases but can be bypassed by translesion synthesis polymerases in the nucleus. Although acrolein-induced adducts are likely to be formed and persist in mitochondrial DNA, animal cell mitochondria lack specialized translesion DNA synthesis polymerases to tolerate these lesions. Thus, it is important to understand how pol γ, the sole mitochondrial DNA polymerase in human cells, acts on acrolein-adducted DNA. To address this question, we investigated the ability of pol γ to bypass the minor groove γ-HOPdG and major groove γ-HOPdA adducts using single nucleotide incorporation and primer extension analyses. The efficiency of pol γ-catalyzed bypass of γ-HOPdG was low, and surprisingly, pol γ preferred to incorporate purine nucleotides opposite the adduct. Pol γ also exhibited ∼2-fold lower rates of excision of the misincorporated purine nucleotides opposite γ-HOPdG compared with the corresponding nucleotides opposite dG. Extension of primers from the termini opposite γ-HOPdG was accomplished only following error-prone purine nucleotide incorporation. However, pol γ preferentially incorporated dT opposite the γ-HOPdA adduct and efficiently extended primers from the correctly paired terminus, indicating that γ-HOPdA is probably nonmutagenic. In summary, our data suggest that acrolein-induced exocyclic DNA lesions can be bypassed by mitochondrial DNA polymerase but, in the case of the minor groove γ-HOPdG adduct, at the cost of unprecedented high mutation rates.

  13. The extreme deuteration of formaldehyde toward IRAS 16293-2422 as probed by ALMA

    NASA Astrophysics Data System (ADS)

    Vilhelm Persson, Magnus; van Dishoeck, Ewine; Coutens, Audrey; Jorgensen, Jes K.; Taquet, Vianney; Furuya, Kenji

    2015-08-01

    Formaldehyde (H2CO) is a molecule that forms efficiently both in the gas-phase and on grains at low temperatures. In the solar-type protostar IRAS 16293-2422 formaldehyde has been shown to have a very high degree of deuteration (HDCO/H2CO: 10-15% e.g. van Dishoeck+1995, Loinard+2000, 2001), including the detection of extended doubly deuterated formaldehyde at a level of 3~16% (Ceccarelli et al. 2001). These high levels can only be explained by grain surface reactions in a cold phase. Previous studies have used single-dish telescopes, which pick up emission from both the hot core and the large scale envelope as demonstrated previously for the deuteration of water with ALMA and PdBI data (Persson+2013, 2014, Coutens+2014). This could have a large effect on the derived abundances for the inner envelope. High-angular resolution observations using ALMA and PdBI/NOEMA are needed to properly derive the deuteration of water in the inner envelope (Persson+2013, 2014). In this study we use ALMA observations of IRAS 16293-2422 on formaldehyde. We derive the amount of deuteration for formaldehyde on small scales, and compare it with water and methanol on similar scales. In particular, we check whether the puzzling high D2O/HDO ratio compared with HDO/H2O found by Coutens+2014 also holds for formaldehyde. Multilayer gas-grain models based on laboratory experiments are used to interpret the data (e.g. Taquet+2014).

  14. [Enhanced porcine interferon-alpha production by Pichia pastoris by methanol/sorbitol co-feeding and energy metabolism shift].

    PubMed

    Wang, Huihui; Jin, Hu; Gao, Minjie; Dai, Keke; Dong, Shijuan; Yu, Ruisong; Li, Zhen; Shi, Zhongping

    2012-02-01

    Porcine interferon-alpha (pIFN-alpha) fermentative production by recombinant Pichia pastoris was carried out in a 10-L bioreactor to study its metabolism changes and effects on fermentation under different inducing strategies, by analyzing the change patterns of the corresponding metabolism and energy regeneration. The results show that the specific activities of alcohol oxidase (AOX), formaldehyde dehydrogenase (FLD) and formate dehydrogenase (FDH) largely increased when reducing temperature from 30 degrees C to 20 degrees C under pure methanol induction, leading significant enhancements in methanol metabolism, formaldehyde dissimilatory energy metabolism and pIFN-alpha antiviral activity. The highest pIFN-alpha antiviral activity reached 1.4 x 10(6) IU/mL, which was about 10-folds of that obtained under 30 degrees C induction. Using methanol/sorbitol co-feeding strategy at 30 degrees C, the major energy metabolism energizing pIFN-alpha synthesis shifted from formaldehyde dissimilatory energy metabolism pathway to TCA cycle, formaldehyde dissimilatory pathway was weakened and accumulation of toxic intermediate metabolite-formaldehyde was relieved, and methanol flux distribution towards to pIFN-alpha synthesis was enhanced. Under this condition, the highest pIFN-alpha antiviral activity reached 1.8 x 10(7) IU/mL which was about 100-folds of that obtained under pure methanol induction at 30 degrees C. More important, enhanced pIFN-alpha production with methanol/sorbitol co-feeding strategy could be implemented under mild conditions, which greatly reduced the fermentation costs and improved the entire fermentation performance.

  15. Isolation and characterization of formaldehyde-degrading fungi and its formaldehyde metabolism.

    PubMed

    Yu, Diansi; Song, Lili; Wang, Wei; Guo, Changhong

    2014-05-01

    Formaldehyde is classified as a human carcinogen that may cause nasopharyngeal cancer and probably leukemia. The effects of environmental and nutritional factors on fungal growth and the biodegradation of formaldehyde were investigated. Fungal strains SGFA1 and SGFA3 isolated from untreated sewage sediment samples collected from heavily formaldehyde-contaminated areas were identified using morphological characteristics and molecular techniques and named as Aspergillus nomius SGFA1 and Penicillium chrysogenum SGFA3. Results indicate that SGFA1 and SGFA3 completely consumed 3,000 and 900 mg l(-1) of formaldehyde, respectively, within 7 days under optimized conditions. Quantitative real-time PCR analyses and enzyme activity analyses demonstrated that glutathione-dependent formaldehyde dehydrogenase (GDFADH) and formate dehydrogenase (FDH) pathway may play a functional role in enhancing formaldehyde-degrading capability in SGFA1. Both fungi have potential use for remediation of formaldehyde pollution.

  16. Density functional theory study of O-H and C-H bond scission of methanol catalyzed by a chemisorbed oxygen layer on Cu(111)

    NASA Astrophysics Data System (ADS)

    Li, Jonathan; Zhou, Guangwen

    2016-04-01

    Using the density-functional theory within the generalized gradient approximation, we have studied the partial oxidation of methanol on a Cu(111) surface covered with a chemisorbed oxygen layer that resembles a Cu2O layer. Adsorption energies and geometries were computed for methanol, methoxy, hydroxymethyl and formaldehyde on both clean Cu(111) and Cu2O/Cu(111) and electronic structures were computed for the reaction intermediates on Cu2O/Cu(111). We also calculated the energy barrier for partial oxidation of methanol to formaldehyde on Cu2O/Cu(111). These results show that the Cu2O monolayer slightly lowers the stability of each of the surface adsorbates and the oxygen strongly promotes hydrogen dissociation by lowering the energy barrier of methanol decomposition and causing the spontaneous dissociation of methanol into methoxy.

  17. Formaldehyde, aspartame, and migraines: a possible connection.

    PubMed

    Jacob, Sharon E; Stechschulte, Sarah

    2008-01-01

    Aspartame is a widely used artificial sweetener that has been linked to pediatric and adolescent migraines. Upon ingestion, aspartame is broken, converted, and oxidized into formaldehyde in various tissues. We present the first case series of aspartame-associated migraines related to clinically relevant positive reactions to formaldehyde on patch testing.

  18. Formaldehyde concentrations in biology department teaching facilities

    SciTech Connect

    Korky, J.K.; Schwarz, S.R.; Lustigman, B.K.

    1987-05-01

    As students and faculty in the biological sciences can attest, low grade exposure to formaldehyde by skin contact and inhalation during dissection is quite irritating. Health effects noted upon exposure to formaldehyde at concentrations of 0.1 to 5 ppm are burning of the eyes, lacrimation, and general irritation to the upper respiratory passages. Symptoms reported for higher exposures, 10 to 20 ppm, include coughing, tightening of the chest, headache and palpitation of the heart. Long exposures at 50 to 100 ppm or more might result in pulmonary edema, pneumonitis, and even death. There is also concern with regard to potential long term detrimental effects. Formaldehyde has been cited as a possible carcinogen in animals. It is a known mutagen in laboratory experimental systems involving Drosophilia, grasshoppers, flowering plants, fungi and bacteria. Animal testing has led investigators to postulate that the primary damage resulting from formaldehyde exposure may involve DNA synthesis and ribosomal RNA transcription. The National Institute of Occupational Safety and Health Administration (NIOSH) investigators have been studying occupational exposure to formaldehyde for over a decade in a variety of industries. This study was undertaken to assess formaldehyde concentrations in biology department dissecting facilities in the 1982-1983 academic year in order if routine dissection produces levels of formaldehyde which were unsafe according to NIOSH and OSHA standards. Chronic formaldehyde exposure is cause for greater concern than incidental exposure.

  19. Acrolein-an α,β-Unsaturated Aldehyde: A Review of Oral Cavity Exposure and Oral Pathology Effects.

    PubMed

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

    2016-01-01

    Acrolein is a highly reactive unsaturated aldehyde widely present in the environment, particularly as a product of tobacco smoke. Our previous studies indicated the adverse consequences of even short-term acrolein exposure and proposed a molecular mechanism of its potential harmful effect on oral cavity keratinocytic cells. In this paper we chose to review the broad spectrum of acrolein sources such as pollution, food, and smoking. Consequently, in this paper we consider a high level of oral exposure to acrolein through these sources and discuss the noxious effects it has on the oral cavity including on salivary quality and contents, oral resistance to oxidative stress, and stress mechanism activation in a variety of oral cells. PMID:27487309

  20. Dietary methanol and autism.

    PubMed

    Walton, Ralph G; Monte, Woodrow C

    2015-10-01

    The authors sought to establish whether maternal dietary methanol during pregnancy was a factor in the etiology of autism spectrum disorders. A seven item questionnaire was given to women who had given birth to at least one child after 1984. The subjects were solicited from a large primary care practice and several internet sites and separated into two groups - mothers who had given birth to a child with autism and those who had not. Average weekly methanol consumption was calculated based on questionnaire responses. 550 questionnaires were completed by women who gave birth to a non-autistic child. On average these women consumed 66.71mg. of methanol weekly. 161 questionnaires were completed by women who had given birth to an autistic child. The average estimated weekly methanol consumption for this group was 142.31mg. Based on the results of the Wilcoxon rank sum-test, we see a significant difference between the reported methanol consumption rates of the two groups. This study suggests that women who have given birth to an autistic child are likely to have had higher intake of dietary sources of methanol than women who have not. Further investigation of a possible link of dietary methanol to autism is clearly warranted.

  1. [Formaldehyde sediment in incubators following disinfection].

    PubMed

    Wartner, R; Kegel, M; Meyer, H D; Schlüter, G; Wegner, J; Werner, E

    1983-12-01

    Measurements in incubators revealed the presence of formaldehyde concentrations involving a health risk for premature and normal newborns kept and cared for in incubators. Prior to measurements, the incubators had been disinfected by means of formaldehyde vapours in an "Aseptor" disinfecting cabinet (Drägerwerk AG, Lübeck) and then ventilated in strict adherence to operating instructions. The elevated formaldehyde concentrations found had been due to residues of paraformaldehyde and urotropin on the surfaces of the disinfected apparatus, liberating formaldehyde by hydrolysis depending on temperature and relative humidity. There should be a basic reconsideration of the present practice of incubator disinfection. From experiments with activated-carbon filters in incubators it would seem that there is a chance of reducing such formaldehyde concentrations.

  2. Role of Water in Methanol Photochemistry on Rutile TiO2(110)

    SciTech Connect

    Shen, Mingmin; Henderson, Michael A.

    2012-08-07

    Photochemistry of the molecularly and dissociatively adsorbed forms of methanol on the vacuum-annealed rutile TiO2(110) surface was explored using temperature programmed desorption (TPD), both with and without coadsorbed water. Methoxy, and not methanol, was confirmed as the photochemically active form of adsorbed methanol on this surface. UV irradiation of methoxy-covered TiO2(110) lead to depletion of the methoxy coverage and formation of formaldehyde and a surface OH group. Coadsorbed water did not promote either molecular methanol photochemistry or thermal decomposition of methanol to methoxy. However, terminal OH groups (OHt), prepared by coadsorption of water and oxygen atoms, thermally converted molecularly adsorbed methanol to methoxy at 120 K, thus enabling photoactivity. While chemisorbed water molecules had no influence on methoxy photochemistry, water molecules hydrogen-bonded in the second layer to bridging oxygen (Obr) sites inhibited the methoxy photodecomposition to formaldehyde. From this we conclude that Obr sites accept protons from the hole-mediated conversion of methoxy to formaldehyde. These results provide new fundamental understanding of the hole-scavenging role of methanol in photochemical processes on TiO2-based materials and how water influences this photochemistry. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle under contract DEAC05-76RL01830. The research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

  3. Electrocatalytic and photocatalytic conversion of CO(2) to methanol using ruthenium complexes with internal pyridyl cocatalysts.

    PubMed

    Boston, David J; Pachón, Yeimi M Franco; Lezna, Reynaldo O; de Tacconi, N R; MacDonnell, Frederick M

    2014-07-01

    The ruthenium complexes [Ru(phen)2(ptpbα)](2+) (Ruα) and [Ru(phen)2(ptpbβ)](2+) (Ruβ), where phen =1,10-phenanthroline ; ptpbα = pyrido[2',3':5,6]pyrazino[2,3-f][1,10]phenanthroline; ptpbβ = pyrido[3',4':5,6]pyrazino[2,3-f][1,10]phenanthroline, are shown as electrocatalysts and photocatalysts for CO2 reduction to formate, formaldehyde, and methanol. Photochemical activity of both complexes is lost in water but is retained in 1 M H2O in DMF. Controlled current electrolysis of a solution of Ruβ in CO2 saturated DMF:H2O (1 M) yields predominantly methanol over a 6 h period at ∼ -0.60 V versus Ag/AgCl, with traces of formaldehyde. After this time, the potential jumped to -1.15 V producing both methanol and CO as products. Irradiation of Ruβ in a solution of DMF:H2O (1 M) containing 0.2 M TEA (as the sacrificial reductant) yields methanol, formaldehyde, and formate. Identifications of all of the relevant redox and protonated states of the respective complexes were obtained by a combination of voltammetry and differential reflectance measurements. Spectroelectrochemistry was particularly useful to probe the photochemical and electrochemical reduction mechanisms of both complexes as well as the complexes speciation in the absence and presence of CO2. PMID:24909055

  4. Acrolein and Asthma Attack Prevalence in a Representative Sample of the United States Adult Population 2000 – 2009

    PubMed Central

    deCastro, B. Rey

    2014-01-01

    Background Acrolein is an air toxic and highly potent respiratory irritant. There is little epidemiology available, but US EPA estimates that outdoor acrolein is responsible for about 75 percent of non-cancer respiratory health effects attributable to air toxics in the United States, based on the Agency's 2005 NATA (National-Scale Air Toxics Assessment) and acrolein's comparatively potent inhalation reference concentration of 0.02 µg/m3. Objectives Assess the association between estimated outdoor acrolein exposure and asthma attack reported by a representative cross-sectional sample of the adult United States population. Methods NATA 2005 chronic outdoor acrolein exposure estimates at the census tract were linked with residences oif adults (≥18 years old) in the NHIS (National Health Interview Survey) 2000 – 2009 (n = 271,348 subjects). A sample-weighted logistic regression model characterized the association between the prevalence of reporting at least one asthma attack in the 12 months prior to survey interview and quintiles of exposure to outdoor acrolein, controlling for potential confounders. Results In the highest quintile of outdoor acrolein exposure (0.05 – 0.46 µg/m3), there was a marginally significant increase in the asthma attack pOR (prevalence-odds ratio [95% CI]  = 1.08 [0.98∶1.19]) relative to the lowest quintile. The highest quintile was also associated with a marginally significant increase in prevalence-odds (1.13 [0.98∶1.29]) in a model limited to never smokers (n = 153,820). Conclusions Chronic exposure to outdoor acrolein of 0.05 – 0.46 µg/m3 appears to increase the prevalence-odds of having at least one asthma attack in the previous year by 8 percent in a representative cross-sectional sample of the adult United States population. PMID:24816802

  5. Determination of formaldehyde in food and feed by an in-house validated HPLC method.

    PubMed

    Wahed, P; Razzaq, Md A; Dharmapuri, S; Corrales, M

    2016-07-01

    Formalin is carcinogenic and is detrimental to public health. The illegal addition of formalin (37% formaldehyde and 14% methanol) to foods to extend their shelf-life is considered to be a common practice in Bangladesh. The lack of accurate methods and the ubiquitous presence of formaldehyde in foods make the detection of illegally added formalin challenging. With the aim of helping regulatory authorities, a sensitive high performance liquid chromatography method was validated for the quantitative determination of formaldehyde in mango, fish and milk. The method was fit-for-purpose and showed good analytical performance in terms of specificity, linearity, precision, recovery and robustness. The expanded uncertainty was <35%. The validated method was applied to screen samples of fruits, vegetables, fresh fish, milk and fish feed collected from different local markets in Dhaka, Bangladesh. Levels of formaldehyde in food samples were compared with published data. The applicability of the method in different food matrices might mean it has potential as a reference standard method. PMID:26920321

  6. Carbonylation of formaldehyde over ion exchange resin catalysts. 1. Batch reactor studies

    SciTech Connect

    Sang Young Lee; Jae Chang Kim; Jae Sung Lee; Young Gul Kim )

    1993-02-01

    Methyl glycolate was synthesized as a precursor to ethylene glycol from the catalytic carbonylation of formaldehyde followed by esterification with methanol. Various cation exchange polystyrene-sulfonic acid resins showed excellent activity and methyl glycolate selectivity. The perfluorinated sulfonic acid resin Nafion-H showed higher activity per proton site, yet was less effective per weight of the catalyst. The effects of process variables such as pressure, temperature, catalyst loading, and solvent were studied. High CO pressures were required to promote formaldehyde carbonylation relative to side reactions between formaldehyde. The presence of water reduced the reaction rate, yet improved the selectivity to methyl glycolate. 1,4-Dioxane was found to be the best solvent in the presence of water. At 135 C, 3,500 psig, and reactant mole ratio of HCHO:H[sub 2]O:H[sup +] = 10:10:1, complete conversion of formaldehyde was achieved in 2-4 h with selectivities of methyl glycolate better than 80%. Catalysts did not show any significant deterioration in performance in repeated use up to 10 batches.

  7. Determination of formaldehyde in food and feed by an in-house validated HPLC method.

    PubMed

    Wahed, P; Razzaq, Md A; Dharmapuri, S; Corrales, M

    2016-07-01

    Formalin is carcinogenic and is detrimental to public health. The illegal addition of formalin (37% formaldehyde and 14% methanol) to foods to extend their shelf-life is considered to be a common practice in Bangladesh. The lack of accurate methods and the ubiquitous presence of formaldehyde in foods make the detection of illegally added formalin challenging. With the aim of helping regulatory authorities, a sensitive high performance liquid chromatography method was validated for the quantitative determination of formaldehyde in mango, fish and milk. The method was fit-for-purpose and showed good analytical performance in terms of specificity, linearity, precision, recovery and robustness. The expanded uncertainty was <35%. The validated method was applied to screen samples of fruits, vegetables, fresh fish, milk and fish feed collected from different local markets in Dhaka, Bangladesh. Levels of formaldehyde in food samples were compared with published data. The applicability of the method in different food matrices might mean it has potential as a reference standard method.

  8. Increased levels of 4-hydroxynonenal and acrolein in the brain in preclinical Alzheimer’s disease (PCAD)

    PubMed Central

    Bradley, M. A.; Markesbery, W. R.

    2010-01-01

    Previous studies demonstrate increased levels of 4-hydroxynonenal (HNE) and acrolein in vulnerable brain regions of subjects with mild cognitive impairment (MCI) and late-stage Alzheimer’s disease (AD). Recently preclinical AD (PCAD) subjects, who demonstrate normal antemortem neuropsychological test scores but abundant AD pathology at autopsy, have become the focus of increased study. Levels of extractable HNE and acrolein were quantified by gas chromatography mass spectrometry with negative chemical ionization and protein-bound HNE and acrolein was quantified by dot-blot immunohistochemistry in the hippocampus/parahippocampal gyrus (HPG), superior and middle temporal gyri (SMTG), and cerebellum (CER) of 10 PCAD and 10 age-matched normal control (NC) subjects. Results of the analyses show a significant (p < 0.05) increase in levels of extractable acrolein in HPG of PCAD subjects compared to age-matched NC subjects and a significant decrease of extractable acrolein in PCAD CER. A significant increase in protein-bound HNE in HPG and a significant decrease in CER of PCAD subjects compared to NC subjects was observed. No significant alterations were observed in either extractable or protein-bound HNE or acrolein in the SMTG of PCAD subjects. Additionally, no significant differences in levels of protein carbonyls were observed in the HPG, SMTG, or CER of PCAD subjects compared to NC subjects. PMID:20171275

  9. 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.

  10. Acrolein, a highly toxic aldehyde generated under oxidative stress in vivo, aggravates the mouse liver damage after acetaminophen overdose.

    PubMed

    Arai, Tomoya; Koyama, Ryo; Yuasa, Makoto; Kitamura, Daisuke; Mizuta, Ryushin

    2014-01-01

    Although acetaminophen-induced liver injury in mice has been extensively studied as a model of human acute drug-induced hepatitis, the mechanism of liver injury remains unclear. Liver injury is believed to be initiated by metabolic conversion of acetaminophen to the highly reactive intermediate N-acetyl p-benzoquinoneimine, and is aggravated by subsequent oxidative stress via reactive oxygen species (ROS), including hydrogen peroxide (H2O2) and the hydroxyl radical (•OH). In this study, we found that a highly toxic unsaturated aldehyde acrolein, a byproduct of oxidative stress, has a major role in acetaminophen-induced liver injury. Acetaminophen administration in mice resulted in liver damage and increased acrolein-protein adduct formation. However, both of them were decreased by treatment with N-acetyl-L-cysteine (NAC) or sodium 2-mercaptoethanesulfonate (MESNA), two known acrolein scavengers. The specificity of NAC and MESNA was confirmed in cell culture, because acrolein toxicity, but not H2O2 or •OH toxicity, was inhibited by NAC and MESNA. These results suggest that acrolein may be more strongly correlated with acetaminophen-induced liver injury than ROS, and that acrolein produced by acetaminophen-induced oxidative stress can spread from dying cells at the primary injury site, causing damage to the adjacent cells and aggravating liver injury.

  11. Methanol Cannon Demonstrations Revisited.

    ERIC Educational Resources Information Center

    Dolson, David A.; And Others

    1995-01-01

    Describes two variations on the traditional methanol cannon demonstration. The first variation is a chain reaction using real metal chains. The second example involves using easily available components to produce sequential explosions that can be musical in nature. (AIM)

  12. The Methanol Multibeam Survey

    NASA Astrophysics Data System (ADS)

    Green, James A.; Cohen, R. J.; Caswell, J. L.; Fuller, G. A.; Brooks, K.; Burton, M. G.; Chrysostomou, A.; Diamond, P. J.; Ellingsen, S. P.; Gray, M. D.; Hoare, M. G.; Masheder, M. R. W.; McClure-Griffiths, N.; Pestalozzi, M.; Phillips, C.; Quinn, L.; Thompson, M. A.; Voronkov, M.; Walsh, A.; Ward-Thompson, D.; Wong-McSweeney, D.; Yates, J. A.; Cox, J.

    2007-03-01

    A new 7-beam methanol multibeam receiver is being used to survey the Galaxy for newly forming massive stars, that are pinpointed by strong methanol maser emission at 6.668 GHz. The receiver, jointly constructed by Jodrell Bank Observatory (JBO) and the Australia Telescope National Facility (ATNF), was successfully commissioned at Parkes in January 2006. The Parkes-Jodrell survey of the Milky Way for methanol masers is two orders of magnitude faster than previous systematic surveys using 30-m class dishes, and is the first systematic survey of the entire Galactic plane. The first 53 days of observations with the Parkes telescope have yielded 518 methanol sources, of which 218 are new discoveries. We present the survey methodology as well as preliminary results and analysis.

  13. Involvement of interleukin-6-regulated nitric oxide synthase in hemorrhagic cystitis and impaired bladder contractions in young rats induced by acrolein, a urinary metabolite of cyclophosphamide.

    PubMed

    Wang, Ching-Chia; Weng, Te-I; Wu, En-Ting; Wu, Mei-Hwan; Yang, Rong-Sen; Liu, Shing-Hwa

    2013-01-01

    Hemorrhagic cystitis is a common complication in children receiving cyclophosphamide, a chemotherapeutic alkylating agent. Acrolein is a urinary metabolite from cyclophosphamide and can induce hemorrhagic cystitis. Here, we investigated the effects and mechanisms of acrolein by intravesical instillation on urinary bladder muscle contractions and pathological alterations in rats. Acrolein instillation significantly increased the muscle contractions of rat bladder detrusor after 1 and 6 h but markedly decreased detrusor contractions after 24 h. Acrolein increased phosphorylated protein kinase C (pan-PKC) expressions in bladders after 1 and 6 h but inhibited it after 24 h. Inducible nitric oxide (NO) synthase (iNOS) protein expressions were markedly induced in bladders 24 h after acrolein treatment. Twenty-four-hour acrolein instillation increased the levels of nitrite/nitrate and interleukin-6 (IL-6) in the urinary bladder. The iNOS inhibitors significantly inhibited the acrolein-increased nitrite/nitrate levels, but not IL-6 levels. IL-6-neutralizing antibodies effectively inhibited the acrolein-increased NOx levels. The increased detrusor contractions by 1-h acrolein treatment were significantly reversed by the PKC inhibitor RO32-0432, and the decreased detrusor contractions by 24-h acrolein treatment were significantly reversed by the iNOS inhibitor and IL-6-neutralizing antibody. Both the iNOS inhibitor and IL-6-neutralizing antibody effectively reversed the increased iNOS expression, decreased PKC phosphorylation, increased bladder weight, and hemorrhagic cystitis in rats 24 h after acrolein treatment. Taken together, these results suggest that an IL-6-regulated iNOS/NO signaling pathway participates in the acrolein-triggered detrusor contraction inhibition and hemorrhagic cystitis. These findings may help us to find a new strategy to treat cyclophosphamide-induced hemorrhagic cystitis.

  14. Service life of respirator cartridges for formaldehyde

    SciTech Connect

    Nelson, G.O.; Carlson, G.J.; Johnson, J.S.

    1981-11-20

    To date there is no NIOSH-approved air-purifying respirator which will effectively remove formaldehyde gas. Because of formaldehyde's high vapor pressure, service life values calculated using the adsorption isotherm and Wheeler equations indicate that organic vapor cartridges containing activated carbon will last less than 10 minutes at concentrations greater than 10 ppM. Studies were initiated to identify a suitable sorbent for this potentially dangerous material. The project involves the following steps: develop a method for producing relatively high concentrations (20 ppM) of a formaldehyde test mixture; verify this test concentration using the NIOSH-approved chromotropic acid wet chemical technique; and survey a wide variety of sorbents, both plain and impregnated, in hopes of identifying a suitable air-purifying cartridge for formaldehyde. A dynamic formaldehyde generation system was fabricated in which formaldehyde was produced by continuously injecting formalin using a syringe pump. The concentration was monitored using an infrared analyzer and checked using the chromotropic acid technique. Twenty-five cartridges were tested for service life at concentrations of formaldehyde gas from 7.1 to 14.8 ppM. Acid gas cartridges and those containing Pittsburgh FCA or ASC showed superior service life.

  15. Formaldehyde Exposures in a University Anatomy Laboratory

    NASA Astrophysics Data System (ADS)

    Winkler, Kyle William

    Air sampling studies were conducted within a university anatomical laboratory during the embalmment of a cadaver in order to determine if dangerous concentrations of formaldehyde existed. Three air sampling studies were conducted in the anatomical laboratory on three separate days that a cadaver was being embalmed. Samples were collected and analyzed using the Occupational Safety and Health Administration (OSHA) Sampling and Analytical Methods: Method 52. Each air sampling study sampled for short term exposure limit (STEL) and time weighted mean (TWA) breathing zone formaldehyde concentrations as well as area TWA formaldehyde concentrations. A personal aldehyde monitor was also used in each air sampling study to sample for breathing zone formaldehyde concentrations. Measured TWA mean exposures to formaldehyde ranged from 0.15--1.3 parts per million (ppm), STEL formaldehyde exposures ranged from 0.019--0.64 ppm, and eight-hour TWAs ranged from 0.03 to 3.6 ppm. All 8-hour TWA formaldehyde concentrations sampled in the anatomy laboratory during an embalmment were less than the permissible exposure limit (PEL) required by OSHA.

  16. Mechanisms of CDDO-imidazolide-mediated cytoprotection against acrolein-induced neurocytotoxicity in SH-SY5Y cells and primary human astrocytes.

    PubMed

    Speen, Adam; Jones, Colton; Patel, Ruby; Shah, Halley; Nallasamy, Palanisamy; Brooke, Elizabeth A S; Zhu, Hong; Li, Y Robert; Jia, Zhenquan

    2015-10-01

    Acrolein is a ubiquitous unsaturated aldehyde has been implicated in the pathogenesis of various neurological disorders. However, limited study has been conducted into potential therapeutic protection and underlying mechanism against acrolein-induced cytotoxicity via upregulation of cellular aldehyde-detoxification defenses. In this study we have utilized RA-differentiated human SH-SY5Y cells and primary human astrocytes to investigate the induction of glutathione (GSH) by the synthetic triterpenoid 2-cyano-3,12-dixooleana-1,9-dien-28-imidazolide (CDDO-Im) and the protective effects CDDO-Im-mediated antioxidant defenses on acrolein toxicity. Acrolein exposure to RA-differentiated SH-SY5Y cells resulted in a significant time dependent depletion of cellular GSH preceding a reduction in cell viability and LDH release. Further, we demonstrated the predominance of cellular GSH in protection against acrolein-induced cytotoxicity. Buthionine sulfoximine (BSO) at 25μM dramatically depleted GSH and significantly potentiated acrolein-induced cytotoxicity. Pretreatment of the cells with 100nM CDDO-Im afforded a dramatic protection against acrolein-induced cytotoxicity. Pretreatment of BSO and CDDO was found to prevent the CDDO-Im-mediated GSH induction and partially reversed the cytoprotective effects of CDDO-Im against acrolein cytotoxicity. Overall, this study represents for the first time the CDDO-Im mediated upregulation of GSH is a predominant mechanism against acrolein-induced neurotoxicity.

  17. Urea formaldehyde foam: a dangerous insulation

    SciTech Connect

    Keough, C.

    1980-12-01

    Insulating a home with urea formaldehyde foam can lead to severe health problems due to poisoning from formaldehyde gas. Respiratory problems, allergies, memory loss, and mental problems can result from exposure to foam insulation fumes. Research is now under way at the Chemical Industry Inst., Univ. of Washington, and other institutions to learn more about the health effects of formaldehyde foam and to develop possible remedies to these problems. Several states are either banning or controlling the use of this type of home insulation.

  18. Anticancer system created by acrolein and hydroxyl radical generated in enzymatic oxidation of spermine and other biochemical reactions.

    PubMed

    Alarcon, R A

    2012-10-01

    A hypothesis suggesting the existence of a ubiquitous physiological anticancer system created by two highly reactive oxidative stress inducers with anticancer properties, acrolein and hydroxyl radical, is reported in this communication. Both components can originate separately or together in several biochemical interactions, among them, the enzymatic oxidation of the polyamine spermine, which appear to be their main source. The foundations of this hypothesis encompass our initial search for growth-inhibitors or anticancer compounds in biological material leading to the isolation of spermine, a polyamine that became highly cytotoxic through the generation of acrolein, when enzymatically oxidized. Findings complemented with pertinent literature data by other workers and observed anticancer activities by sources capable of producing acrolein and hydroxyl radical. This hypothesis obvious implication: spermine enzymatic oxidations or other biochemical interactions that would co-generate acrolein and hydroxyl radical, the anticancer system components, should be tried as treatments for any given cancer. The biochemical generation of acrolein observed was totally unexpected, since this aldehyde was known; as a very toxic and highly reactive xenobiotic chemical produced in the pyrolysis of fats and other organic material, found as an atmospheric pollutant, in tobacco smoke and car emissions, and mainly used as a pesticide or aquatic herbicide. Numerous studies on acrolein, considered after our work a biological product, as well, followed. In them, acrolein widespread presence, its effects on diverse cellular proteins, such as, growth factors, and its anticancer activities, were additionally reported. Regarding hydroxyl radical, the second component of the proposed anticancer system, and another cytotoxic product in normal cell metabolism, it co-generates with acrolein in several biochemical interactions, occurrences suggesting that these products might jointly fulfill some

  19. Thiolation of protein-bound carcinogenic aldehyde. An electrophilic acrolein-lysine adduct that covalently binds to thiols.

    PubMed

    Furuhata, Atsunori; Nakamura, Mitsuhiro; Osawa, Toshihiko; Uchida, Koji

    2002-08-01

    Acrolein, a representative carcinogenic aldehyde that could be ubiquitously generated in biological systems under oxidative stress, shows facile reactivity with the epsilon-amino group of lysine to form N(epsilon)-(3-formyl-3,4-dehydropiperidino)lysine (FDP-lysine) as the major product (Uchida, K., Kanematsu, M., Morimitsu, Y., Osawa, T., Noguchi, N., and Niki, E. (1998) J. Biol. Chem. 273, 16058-16066). In the present study, we determined the electrophilic potential of FDP-lysine and established a novel mechanism of protein thiolation in which the FDP-lysine generated in the acrolein-modified protein reacts with sulfhydryl groups to form thioether adducts. When a sulfhydryl enzyme, glyceraldehyde-3-phosphate dehydrogenase, was incubated with acrolein-modified bovine serum albumin in sodium phosphate buffer (pH 7.2) at 37 degrees C, a significant loss of sulfhydryl groups, which was accompanied by the loss of enzyme activity and the formation of high molecular mass protein species (>200 kDa), was observed. The FDP-lysine adduct generated in the acrolein-modified protein was suggested to represent a thiol-reactive electrophile based on the following observations. (i) N(alpha)-acetyl-FDP-lysine, prepared from the reaction of N(alpha)-acetyl lysine with acrolein, was covalently bound to glyceraldehyde-3-phosphate dehydrogenase. (ii) The FDP-lysine derivative reacted with glutathione to form a GSH conjugate. (iii) The acrolein-modified bovine serum albumin significantly reacted with GSH to form a glutathiolated protein. Furthermore, the observation that the glutathiolated acrolein-modified protein showed decreased immunoreactivity with an anti-FDP-lysine monoclonal antibody suggested that the FDP-lysine residues in the acrolein-modified protein served as the binding site of GSH. These data suggest that thiolation of the protein-bound acrolein may be involved in redox alteration under oxidative stress, whereby oxidative stress generates the increased production of

  20. Detection of acrolein and acrylonitrile with a pulsed room temperature quantum cascade laser

    NASA Astrophysics Data System (ADS)

    Manne, J.; Jäger, W.; Tulip, J.

    2010-06-01

    We investigated the use of a pulsed, distributed feedback quantum cascade laser centered at 957 cm-1 in combination with an astigmatic Herriot cell with 250 m path length for the detection of acrolein and acrylonitrile. These molecules have been identified as hazardous air-pollutants because of their adverse health effects. The spectrometer utilizes the intra-pulse method, where a linear frequency down-chirp, that is induced when a top-hat current pulse is applied to the laser, is used for sweeping across the absorption line. Up to 450 ns long pulses were used for these measurements which resulted in a spectral window of ~2.2 cm-1. A room temperature mercury-cadmium-telluride detector was used, resulting in a completely cryogen free spectrometer. We demonstrated detection limits of ~3 ppb for acrylonitrile and ~6 ppb for acrolein with ~10 s averaging time. Laser characterization and optimization of the operational parameters for sensitivity improvement are discussed.

  1. Catalytic behavior of Group VIII transition metals in the deuterium-acrolein reaction

    SciTech Connect

    Touroude, R.

    1980-09-01

    The catalytic reactions between acrolein and deuterium over all the Group VIII transition metals were studied by microwave spectrometry. A high catalyst selectivity in the exchange reaction, in which hydrogen is replaced by deuterium in acrolein, was found. Over Rh, Pd, Ir, Ru, and Ni, hydrogens situated on the ..beta.. carbon were quasi-selectively exchanged while over Pt, Os, and especially Co, an additional exchange of the aldehydic hydrogen took place. Over Fe, the hydrogen situated on the ..cap alpha.. carbon and the aldehydic hydrogen were exchanged equally. An attempt is made to relate the nature of the exchange to hydrogenation, decarbonylation, and hydrogenolysis and several reaction mechanisms are proposed in addition to the classical Horiuti-Polanyi mechanism, which is restricted to hydrogenation of the C-C double bond.

  2. Solar photocatalytic conversion of CO{sub 2} to methanol

    SciTech Connect

    Ryba, G.; Shelnutt, J.; Prairie, M.R.; Assink, R.A.

    1997-02-01

    This report summarizes the three-year LDRD program directed at developing catalysts based on metalloporphyrins to reduce carbon dioxide. Ultimately it was envisioned that such catalysts could be made part of a solar-driven photoredox cycle by coupling metalloporphyrins with semiconductor systems. Such a system would provide the energy required for CO{sub 2} reduction to methanol, which is an uphill 6-electron reduction. Molecular modeling and design capabilities were used to engineer metalloporphyrin catalysts for converting CO{sub 2} to CO and higher carbon reduction products like formaldehyde, formate, and methanol. Gas-diffusion electrochemical cells were developed to carry out these reactions. A tin-porphyrin/alumina photocatalyst system was partially developed to couple solar energy to this reduction process.

  3. Evaluation of an EMITEC resistively heated metal monolith catalytic converter on two M100 neat methanol-fueled vehicles

    NASA Astrophysics Data System (ADS)

    Piotrowski, Gregory K.; Schaefer, Ronald M.

    1992-12-01

    The report describes the evaluation of a resistively heated catalyst system on two different methanol fueled vehicles. The EMITEC catalyst consisted of a compact resistively heated metal monolith in front of a larger conventional main converter. The EMITEC catalyst was evaluated on two neat methanol-fueled vehicles, a 1981 Volkswagen Rabbit and a 1988 Toyota Corolla. Emission testing was conducted over the Federal Test Procedure (FTP) CVS-75 test cycle. The emissions of primary interest were cold start methanol (unburned fuel), carbon monoxide, and formaldehyde.

  4. Influenza A infection attenuates relaxation responses of mouse tracheal smooth muscle evoked by acrolein.

    PubMed

    Cheah, Esther Y; Mann, Tracy S; Burcham, Philip C; Henry, Peter J

    2015-02-15

    The airway epithelium is an important source of relaxant mediators, and damage to the epithelium caused by respiratory tract viruses may contribute to airway hyperreactivity. The aim of this study was to determine whether influenza A-induced epithelial damage would modulate relaxation responses evoked by acrolein, a toxic and prevalent component of smoke. Male BALB/c mice were inoculated intranasally with influenza A/PR-8/34 (VIRUS-infected) or allantoic fluid (SHAM-infected). On day 4 post-inoculation, isometric tension recording studies were conducted on carbachol pre-contracted tracheal segments isolated from VIRUS and SHAM mice. Relaxant responses to acrolein (30 μM) were markedly smaller in VIRUS segments compared to SHAM segments (2 ± 1% relaxation vs. 28 ± 5%, n=14, p<0.01). Similarly, relaxation responses of VIRUS segments to the neuropeptide substance P (SP) were greatly attenuated (1 ± 1% vs. 47 ± 6% evoked by 1 nM SP, n=14, p<0.001). Consistent with epithelial damage, PGE2 release in response to both acrolein and SP were reduced in VIRUS segments (>35% reduction, n=6, p<0.01), as determined using ELISA. In contrast, exogenous PGE2 was 2.8-fold more potent in VIRUS relative to SHAM segments (-log EC50 7.82 ± 0.14 vs. 7.38 ± 0.05, n=7, p<0.01) whilst responses of VIRUS segments to the β-adrenoceptor agonist isoprenaline were similar to SHAM segments. In conclusion, relaxation responses evoked by acrolein were profoundly diminished in tracheal segments isolated from influenza A-infected mice. The mechanism through which influenza A infection attenuates this response appears to involve reduced production of PGE2 in response to SP due to epithelial cell loss, and may provide insight into the airway hyperreactivity observed with influenza A infection.

  5. Field and laboratory investigations into the persistence of glutaraldehyde and acrolein in natural gas storage operations

    SciTech Connect

    Morris, E.A. III; Pope, D.H.

    1994-12-31

    The persistence of biocides formulated in glutaraldehyde and acrolein were tested in different produced water environments using a calorimetric general aldehyde detection method based on metaphenylenediamine. The objective of Phase 1 (laboratory study) was to characterize the persistence of acrolein and glutaraldehyde in water samples representative of the environments to which the biocides has been applied. To validate the test results, some duplicate samples were analyzed using gas chromatographic (GC) methods and repeat trials were done on certain tests. The objective of Phase 2 (field assessment) was to compare the Phase 1 results on formation waters to actual field data. At the study site, monitoring of biocide residuals had been done by the chemical vendor at all treated wells. The data provided information on glutaraldehyde and acrolein residuals for one gas withdrawal (winter) season. The data were compiled so that persistence/degradation graphs could be constructed for the biocides in each formation. These field data were then compared to the Phase 1 results. The persistence of the biocides in each environment tested was shown to be unique, but repeatable.

  6. Vapour phase dehydration of glycerol to acrolein over tungstated zirconia catalysts

    NASA Astrophysics Data System (ADS)

    Rao Ginjupalli, Srinivasa; Mugawar, Sowmya; Rajan N., Pethan; Kumar Balla, Putra; Chary Komandur, V. R.

    2014-08-01

    Tetragonal (TZ) and monoclinic (MZ) polymorphs of zirconia supports were synthesised by sol-gel method followed by variation of the calcination temperature. Tungstated (10 wt% WO3) supported on the zirconia polymorphs were prepared by impregnation method by using ammonium metatungstate precursor. The physico-chemical properties of the calcined catalysts were characterised by X-ray diffraction, UV-vis diffused reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), surface area and pore size distribution measurements to gain insight into the effect of morphology of the catalyst textural properties, and structure. The surface acidic properties have been determined by NH3 TPD method and also with FT-IR spectra of pyridine adsorption. Vapour phase dehydration of glycerol to acrolein was employed to investigate the catalytic functionalities. Glycerol conversion and acrolein selectivity was mainly dependent on the fraction of moderate acid sites with majority of them are due to Brønsted acidic sites. Monoclinic zirconia based catalysts have shown the highest activity and acrolein selectivity compared to the corresponding tetragonal zirconia catalysts.

  7. Acrolein inhalation alters arterial blood gases and triggers carotid body-mediated cardiovascular responses in hypertensive rats

    PubMed Central

    Perez, Christina M.; Hazari, Mehdi S.; Ledbetter, Allen D.; Haykal-Coates, Najwa; Carll, Alex P.; Cascio, Wayne E.; Winsett, Darrell W.; Costa, Daniel L.; Farraj, Aimen K.

    2016-01-01

    Context Air pollution exposure affects autonomic function, heart rate, blood pressure and left ventricular function. While the mechanism for these effects is uncertain, several studies have reported that air pollution exposure modifies activity of the carotid body, the major organ that senses changes in arterial oxygen and carbon dioxide levels, and elicits downstream changes in autonomic control and cardiac function. Objective We hypothesized that exposure to acrolein, an unsaturated aldehyde and mucosal irritant found in cigarette smoke and diesel exhaust, would activate the carotid body chemoreceptor response and lead to secondary cardiovascular responses in rats. Materials and methods Spontaneously hypertensive (SH) rats were exposed once for 3 h to 3 ppm acrolein gas or filtered air in whole body plethysmograph chambers. To determine if the carotid body mediated acrolein-induced cardiovascular responses, rats were pretreated with an inhibitor of cystathionine γ-lyase (CSE), an enzyme essential for carotid body signal transduction. Results Acrolein exposure induced several cardiovascular effects. Systolic, diastolic and mean arterial blood pressure increased during exposure, while cardiac contractility decreased 1 day after exposure. The cardiovascular effects were associated with decreases in pO2, breathing frequency and expiratory time, and increases in sympathetic tone during exposure followed by parasympathetic dominance after exposure. The CSE inhibitor prevented the cardiovascular effects of acrolein exposure. Discussion and conclusion Pretreatment with the CSE inhibitor prevented the cardiovascular effects of acrolein, suggesting that the cardiovascular responses with acrolein may be mediated by carotid body-triggered changes in autonomic tone. (This abstract does not reflect EPA policy.) PMID:25600140

  8. Formaldehyde in the Far Outer Galaxy

    NASA Astrophysics Data System (ADS)

    Lugo, S. K.; Magnani, L.; Brand, J.; Wouterloot, J. G. A.

    2006-06-01

    We present results from an initial survey of the 212-111 transition of formaldehyde (H2CO) in the Far Outer Galaxy (galactocentric distances, Rg > 16 kpc). Formaldehyde is a key prebiotic molecule; determining the outermost extent of its distribution can be used to set a limit to the Galaxy's "Habitable Zone", the region where conditions for the formation of life are most favorable. We surveyed 67 clouds in the outer Galaxy ranging 12 - 23 kpc in distance from the Galactic Center. Formaldehyde emission at 140.8 GHz was detected from 44 of 67 lines of sight, including 7 clouds at Rg > 20 kpc. Formaldehyde is readily detectable even in the Far Outer Galaxy beyond the edge of the stellar disk. The widespread distribution of H2CO in the Far Outer Galaxy is a positive first step in determining how favorable are conditions in this large region towards the formation of life.

  9. Formaldehyde derived from dietary aspartame binds to tissue components in vivo.

    PubMed

    Trocho, C; Pardo, R; Rafecas, I; Virgili, J; Remesar, X; Fernández-López, J A; Alemany, M

    1998-01-01

    Adult male rats were given an oral dose of 10 mg/kg aspartame 14C-labelled in the methanol carbon. At timed intervals of up to 6 hours, the radioactivity in plasma and several organs was investigated. Most of the radioactivity found (>98% in plasma, >75% in liver) was bound to protein. Label present in liver, plasma and kidney was in the range of 1-2% of total radioactivity administered per g or mL, changing little with time. Other organs (brown and white adipose tissues, muscle, brain, cornea and retina) contained levels of label in the range of 1/12 to 1/10th of that of liver. In all, the rat retained, 6 hours after administration about 5% of the label, half of it in the liver. The specific radioactivity of tissue protein, RNA and DNA was quite uniform. The protein label was concentrated in amino acids, different from methionine, and largely coincident with the result of protein exposure to labelled formaldehyde. DNA radioactivity was essentially in a single different adduct base, different from the normal bases present in DNA. The nature of the tissue label accumulated was, thus, a direct consequence of formaldehyde binding to tissue structures. The administration of labelled aspartame to a group of cirrhotic rats resulted in comparable label retention by tissue components, which suggests that liver function (or its defect) has little effect on formaldehyde formation from aspartame and binding to biological components. The chronic treatment of a series of rats with 200 mg/kg of non-labelled aspartame during 10 days resulted in the accumulation of even more label when given the radioactive bolus, suggesting that the amount of formaldehyde adducts coming from aspartame in tissue proteins and nucleic acids may be cumulative. It is concluded that aspartame consumption may constitute a hazard because of its contribution to the formation of formaldehyde adducts.

  10. Contribution of formaldehyde to respiratory cancer.

    PubMed Central

    Nelson, N; Levine, R J; Albert, R E; Blair, A E; Griesemer, R A; Landrigan, P J; Stayner, L T; Swenberg, J A

    1986-01-01

    This article reviews the available data on the carcinogenicity of formaldehyde from experimental and epidemiologic studies and makes recommendations for further research. Two definitive chronic inhalation bioassays on rodents have demonstrated that formaldehyde produces nasal cancer in rats and mice at 14 ppm and in rats at 6 ppm, which is within the domain of present permissible human exposure (8-hr time-weighted average of 3 ppm, a 5 ppm ceiling, and a 10 ppm short-term exposure limit). Biochemical and physiologic studies in rats have shown that inhaled formaldehyde can depress respiration, inhibit mucociliary clearance, stimulate cell proliferation, and crosslink DNA and protein in the nasal mucosa. No deaths from nasal cancer have been reported in epidemiologic studies of cohorts exposed to formaldehyde, but three case-control studies suggest the possibility of increased risk. Although excesses of lung cancer deaths have been observed in some studies at industrial plants with formaldehyde exposure, uncertainties in interpretation limit the evaluation of these findings. Excess cancers of the brain and of lymphatic and hematopoietic tissues have been reported in certain studies of industrial groups and in most studies of formaldehyde-exposed professionals, but whether these excesses are related to formaldehyde exposure is not known. Several properties of formaldehyde pose unique problems for future research: the mechanisms responsible for its nonlinear response; its probable mechanism of carcinogenic action as a cross-linking agent; its formation in tissues as a normal metabolite; its possible action as a promoter and/or a cocarcinogen; and the importance of glutathione as a host defense at low exposure. PMID:3830109

  11. Methanol in dark clouds

    NASA Technical Reports Server (NTRS)

    Friberg, P.; Hjalmarson, A.; Madden, S. C.; Irvine, W. M.

    1988-01-01

    The first observation of methanol in cold dark clouds TMC 1, L 134 N, and B 335 is reported. In all three clouds, the relative abundance of methanol was found to be in the range of 10 to the -9th (i.e., almost an order of magnitude more abundant than acetaldehyde), with no observable variation between the clouds. Methanol emission showed a complex velocity structure; in TMC 1, clear indications of non-LTE were observed. Dimethyl ether was searched for in L 134 N; the upper limit of the column density of dimethyl ether in L 134 N was estimated to be 4 x 10 to the 12th/sq cm, assuming 5 K rotation temperature and LTE. This limit makes the abundance ratio (CH3)2O/CH3OH not higher than 1/5, indicating that dimethyl ether is not overabundant in this dark cloud.

  12. HPLC Characterization of Phenol-Formaldehyde Resole Resin Used in Fabrication of Shuttle Booster Nozzles

    NASA Technical Reports Server (NTRS)

    Young, Philip R.

    1999-01-01

    A reverse phase High Performance Liquid Chromatographic method was developed to rapidly fingerprint a phenol-formaldehyde resole resin similar to Durite(R) SC-1008. This resin is used in the fabrication of carbon-carbon composite materials from which Space Shuttle Solid Rocket Booster nozzles are manufactured. A knowledge of resin chemistry is essential to successful composite processing and performance. The results indicate that a high quality separation of over 35 peaks in 25 minutes were obtained using a 15 cm Phenomenex LUNA C8 bonded reverse phase column, a three-way water-acetonitrile-methanol nonlinear gradient, and LTV detection at 280 nm.

  13. Report on the Consensus Workshop on Formaldehyde.

    PubMed Central

    1984-01-01

    The Consensus Workshop on Formaldehyde consisted of bringing together scientists from academia, government, industry and public interest groups to address some important toxicological questions concerning the health effects of formaldehyde. The participants in the workshop, the Executive Panel which coordinated the meeting, and the questions posed, all were chosen through a broadly based nomination process in order to achieve as comprehensive a consensus as possible. The subcommittees considered the toxicological problems associated with formaldehyde in the areas of exposure, epidemiology, carcinogenicity/histology/genotoxicity, immunology/sensitization/irritation, structure activity/biochemistry/metabolism, reproduction/teratology, behavior/neurotoxicity/psychology and risk estimation. Some questions considered included the possible human carcinogenicity of formaldehyde, as well as other human health effects, and the interpretation of pathology induced by formaldehyde. These reports, plus introductory material on the procedures used in setting up the Consensus Workshop are presented here. Additionally, there is included a listing of the data base that was made available to the panel chairmen prior to the meeting and was readily accessible to the participants during their deliberations in the meeting. This data base, since it was computerized, was also capable of being searched for important terms. These materials were supplemented by information brought by the panelists. The workshop has defined the consensus concerning a number of major points in formaldehyde toxicology and has identified a number of major deficits in understanding which are important guides to future research. PMID:6525992

  14. Formaldehyde and skin tumorigenesis in Sencar mice

    SciTech Connect

    Iversen, O.H.

    1988-01-01

    Previous experiments involving topical applications of formaldehyde on hairless mouse skin were repeated with SENCAR mice, which are bred for maximum sensitivity to chemical tumorigenesis. Most experimental groups consisted of 32 mice. Topical skin applications of either 100 ..mu..l acetone of about 200 ..mu..l 4% formaldehyde in water twice weekly, resulted in two tumor-bearing animals, each with one small, benign papilloma. A group of 96 mice, treated once with 51.2 ..mu..g DMBA in acetone, developed a total of 107 tumors in 40 tumor-bearing animals. Thus, DMBA is a strong, complete tumorigen also in SENCAR mice. Animals given 51.2 ..mu..g DMBA first and then treated twice weekly with 1% formaldehyde developed a total of 30 tumors in 8 tumor-bearing animals, whereas mice given 51.2 ..mu..g DMBA first, followed by twice weekly treatment with 4% formaldehyde, developed 51 tumors in 15 animals. When two widely accepted, statistical methods were used, there was no significant difference between the groups treated once with DMBA alone and that treated once with DMBA followed by 4% formaldehyde. The results in SENCAR mice confirm that formaldehyde has no skin tumorigenic or carcinogenic potency of its own. It seems doubtful whether it may act as a very weak enhancer of DMBA-induced tumorigenesis, but it has no significant influence on DMBA-induced carcinogenesis.

  15. XoxF Acts as the Predominant Methanol Dehydrogenase in the Type I Methanotroph Methylomicrobium buryatense

    PubMed Central

    Chu, Frances

    2016-01-01

    ABSTRACT Many methylotrophic taxa harbor two distinct methanol dehydrogenase (MDH) systems for oxidizing methanol to formaldehyde: the well-studied calcium-dependent MxaFI type and the more recently discovered lanthanide-containing XoxF type. MxaFI has traditionally been accepted as the major functional MDH in bacteria that contain both enzymes. However, in this study, we present evidence that, in a type I methanotroph, Methylomicrobium buryatense, XoxF is likely the primary functional MDH in the environment. The addition of lanthanides increases xoxF expression and greatly reduces mxa expression, even under conditions in which calcium concentrations are almost 100-fold higher than lanthanide concentrations. Mutations in genes encoding the MDH enzymes validate our finding that XoxF is the major functional MDH, as XoxF mutants grow more poorly than MxaFI mutants under unfavorable culturing conditions. In addition, mutant and transcriptional analyses demonstrate that the lanthanide-dependent MDH switch operating in methanotrophs is mediated in part by the orphan response regulator MxaB, whose gene transcription is itself lanthanide responsive. IMPORTANCE Aerobic methanotrophs, bacteria that oxidize methane for carbon and energy, require a methanol dehydrogenase enzyme to convert methanol into formaldehyde. The calcium-dependent enzyme MxaFI has been thought to primarily carry out methanol oxidation in methanotrophs. Recently, it was discovered that XoxF, a lanthanide-containing enzyme present in most methanotrophs, can also oxidize methanol. In a methanotroph with both MxaFI and XoxF, we demonstrate that lanthanides transcriptionally control genes encoding the two methanol dehydrogenases, in part by controlling expression of the response regulator MxaB. Lanthanides are abundant in the Earth's crust, and we demonstrate that micromolar amounts of lanthanides are sufficient to suppress MxaFI expression. Thus, we present evidence that XoxF acts as the predominant

  16. Development and application of a sensitive method to determine concentrations of acrolein and other carbonyls in ambient air.

    PubMed

    Cahill, Thomas M; Charles, M Judith; Seaman, Vincent Y

    2010-05-01

    Acrolein, an unsaturated aldehyde, has been identified as one of the most important toxic air pollutants in recent assessments of ambient air quality. Current methods for determining acrolein concentrations, however, suffer from poor sensitivity, selectivity, and reproducibility. The collection and analysis of unsaturated carbonyls, and acrolein in particular, is complicated by unstable derivatives, coelution of similar compounds, and ozone interference. The primary objective of this research was to develop an analytical method to measure acrolein and other volatile carbonyls present in low part-per-trillion concentrations in ambient air samples obtained over short sampling periods. The method we devised uses a mist chamber in which carbonyls from air samples form water-soluble adducts with bisulfite in the chamber solution, effectively trapping the carbonyls in the solution. The mist chamber methodology proved effective, with collection efficiency for acrolein of at least 70% for each mist chamber at a flow rate of approximately 17 L/min. After the sample collection, the carbonyls are liberated from the bisulfite adducts through the addition of hydrogen peroxide, which converts the bisulfite to sulfate, reversing the bisulfite addition reaction. The free carbonyls are then derivatized by o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA*), which stabilizes the analytes and makes them easier to detect by electron-capture negative ionization mass spectrometry (ECNI-MS). The derivatives are then extracted and analyzed by gas chromatography-mass spectrometry (GC-MS). The mist chamber method was applied in a field test to determine the extent of acrolein in ambient air near the Peace Bridge plaza in Buffalo, New York, an area of heavy traffic near a major border crossing between the United States and Canada. In addition, XAD-2 adsorbent cartridges coated with 2-(hydroxymethyl)piperidine (2-HMP) according to Occupational Safety and Health Administration (OSHA) Method

  17. Development and application of a sensitive method to determine concentrations of acrolein and other carbonyls in ambient air.

    PubMed

    Cahill, Thomas M; Charles, M Judith; Seaman, Vincent Y

    2010-05-01

    Acrolein, an unsaturated aldehyde, has been identified as one of the most important toxic air pollutants in recent assessments of ambient air quality. Current methods for determining acrolein concentrations, however, suffer from poor sensitivity, selectivity, and reproducibility. The collection and analysis of unsaturated carbonyls, and acrolein in particular, is complicated by unstable derivatives, coelution of similar compounds, and ozone interference. The primary objective of this research was to develop an analytical method to measure acrolein and other volatile carbonyls present in low part-per-trillion concentrations in ambient air samples obtained over short sampling periods. The method we devised uses a mist chamber in which carbonyls from air samples form water-soluble adducts with bisulfite in the chamber solution, effectively trapping the carbonyls in the solution. The mist chamber methodology proved effective, with collection efficiency for acrolein of at least 70% for each mist chamber at a flow rate of approximately 17 L/min. After the sample collection, the carbonyls are liberated from the bisulfite adducts through the addition of hydrogen peroxide, which converts the bisulfite to sulfate, reversing the bisulfite addition reaction. The free carbonyls are then derivatized by o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA*), which stabilizes the analytes and makes them easier to detect by electron-capture negative ionization mass spectrometry (ECNI-MS). The derivatives are then extracted and analyzed by gas chromatography-mass spectrometry (GC-MS). The mist chamber method was applied in a field test to determine the extent of acrolein in ambient air near the Peace Bridge plaza in Buffalo, New York, an area of heavy traffic near a major border crossing between the United States and Canada. In addition, XAD-2 adsorbent cartridges coated with 2-(hydroxymethyl)piperidine (2-HMP) according to Occupational Safety and Health Administration (OSHA) Method

  18. Acrolein Modification Impairs Key Functional Features of Rat Apolipoprotein E: Identification of Modified Sites by Mass Spectrometry

    PubMed Central

    Tran, Tuyen N.; Kosaraju, Malathi G.; Tamamizu-Kato, Shiori; Akintunde, Olayemi; Zheng, Ying; Bielicki, John K.; Pinkerton, Kent; Uchida, Koji; Lee, Yuan Yu; Narayanaswami, Vasanthy

    2014-01-01

    Apolipoprotein E (apoE), an anti-atherogenic apolipoprotein, plays a significant role in the metabolism of lipoproteins. It lowers plasma lipid levels by acting as a ligand for low-density lipoprotein receptor (LDLr) family of proteins, in addition to playing a role in promoting macrophage cholesterol efflux in atherosclerotic lesions. The objective of this study is to examine the effect of acrolein modification on the structure and function of rat apoE and to determine sites and nature of modification by mass spectrometry. Acrolein is a highly reactive aldehyde, which is generated endogenously as one of the products of lipid peroxidation and is present in the environment in pollutants such as tobacco smoke and heated oils. In initial studies, acrolein-modified apoE was identified by immunoprecipitation using an acrolein-lysine specific antibody, in the plasma of ten-week old male rats that were exposed to filtered air (FA) or low doses of environmental tobacco smoke (ETS). While both groups displayed acrolein-modified apoE in the lipoprotein fraction, the ETS group had higher levels in lipid-free fraction compared to the FA group. This observation provided the rationale to further investigate the effect of acrolein modification on rat apoE at a molecular level. Treatment of recombinant rat apoE with a 10-fold molar excess of acrolein resulted in: (i) a significant decrease in lipid-binding and cholesterol efflux abilities, (ii) impairment in the LDLr- and heparin-binding capabilities, and (iii) significant alterations in the overall stability of the protein. The disruption in the functional abilities is attributed directly or indirectly to acrolein modification yielding: an aldimine adduct at K149 and K155 (+38); a propanal adduct at K135 and K138 (+56); an Nε-(3-methylpyridinium)lysine (MP-lysine) at K64, K67 and K254 (+76), and Nε-(3-formyl-3,4-dehydropiperidino)lysine (FDP-lysine) derivative at position K68 (+94), as determined by Matrix-Assisted Laser

  19. Acrolein modification impairs key functional features of rat apolipoprotein E: identification of modified sites by mass spectrometry.

    PubMed

    Tran, Tuyen N; Kosaraju, Malathi G; Tamamizu-Kato, Shiori; Akintunde, Olayemi; Zheng, Ying; Bielicki, John K; Pinkerton, Kent; Uchida, Koji; Lee, Yuan Yu; Narayanaswami, Vasanthy

    2014-01-21

    Apolipoprotein E (apoE), an antiatherogenic apolipoprotein, plays a significant role in the metabolism of lipoproteins. It lowers plasma lipid levels by acting as a ligand for the low-density lipoprotein receptor (LDLr) family of proteins, in addition to playing a role in promoting macrophage cholesterol efflux in atherosclerotic lesions. The objective of this study is to examine the effect of acrolein modification on the structure and function of rat apoE and to determine the sites and nature of modification by mass spectrometry. Acrolein is a highly reactive aldehyde, which is generated endogenously as one of the products of lipid peroxidation and is present in the environment in pollutants such as tobacco smoke and heated oils. In initial studies, acrolein-modified apoE was identified by immunoprecipitation using an acrolein-lysine specific antibody in the plasma of 10-week old male rats that were exposed to filtered air (FA) or low doses of environmental tobacco smoke (ETS). While both groups displayed acrolein-modified apoE in the lipoprotein fraction, the ETS group had higher levels in the lipid-free fraction compared with the FA group. This observation provided the rationale to further investigate the effect of acrolein modification on rat apoE at a molecular level. Treatment of recombinant rat apoE with a 10-fold molar excess of acrolein resulted in (i) a significant decrease in lipid-binding and cholesterol efflux abilities, (ii) impairment in the LDLr- and heparin-binding capabilities, and (iii) significant alterations in the overall stability of the protein. The disruption in the functional abilities is attributed directly or indirectly to acrolein modification yielding an aldimine adduct at K149 and K155 (+38); a propanal adduct at K135 and K138 (+56); an N(ε)-(3-methylpyridinium)lysine (MP-lysine) at K64, K67, and K254 (+76), and an N(ε)-(3-formyl-3,4-dehydropiperidino)lysine (FDP-lysine) derivative at position K68 (+94), as determined by matrix

  20. Hypoxia stress test reveals exaggerated cardiovascular effects in hypertensive rats after exposure to the air pollutant acrolein.

    PubMed

    Perez, Christina M; Ledbetter, Allen D; Hazari, Mehdi S; Haykal-Coates, Najwa; Carll, Alex P; Winsett, Darrell W; Costa, Daniel L; Farraj, Aimen K

    2013-04-01

    Exposure to air pollution increases the risk of cardiovascular morbidity and mortality, especially in susceptible populations. Despite increased risk, adverse responses are often delayed and require additional stress tests to reveal latent effects of exposure. The goal of this study was to use an episode of "transient hypoxia" as an extrinsic stressor to uncover latent susceptibility to environmental pollutants in a rodent model of hypertension. We hypothesized that exposure to acrolein, an unsaturated aldehyde and mucosal irritant found in cigarette smoke, diesel exhaust, and power plant emissions, would increase cardiopulmonary sensitivity to hypoxia, particularly in hypertensive rats. Spontaneously hypertensive and Wistar Kyoto (normotensive) rats, implanted with radiotelemeters, were exposed once for 3h to 3 ppm acrolein gas or filtered air in whole-body plethysmograph chambers and challenged with a 10% oxygen atmosphere (10min) 24h later. Acrolein exposure increased heart rate, blood pressure, breathing frequency, and minute volume in hypertensive rats and also increased the heart rate variability parameter LF, suggesting a potential role for increased sympathetic tone. Normotensive rats only had increased blood pressure during acrolein exposure. The hypoxia stress test after acrolein exposure revealed increased diastolic blood pressure only in hypertensive rats and increased minute volume and expiratory time only in normotensive rats. These results suggest that hypertension confers exaggerated sensitivity to air pollution and that the hypoxia stress test is a novel tool to reveal the potential latent effects of air pollution exposure.

  1. Time and dose effects of cigarette smoke and acrolein on protein carbonyl formation in HaCaT keratinocytes.

    PubMed

    Avezov, K; Reznick, A Z; Aizenbud, D

    2015-01-01

    Cigarette smoke (CS) is an important environmental source of human exposure to a highly toxic and chemically active α,β-unsaturated aldehyde: acrolein. It is capable of causing protein carbonylation and dysfunction, especially in oral tissues of smokers, constantly exposed to CS toxic constituents. The foremost damage is considered to be cumulative, but even a short exposure can be potentially harmful. The objectives of the current study were to examine the short time and dose effects of direct CS and acrolein exposure on intracellular protein carbonylation in epithelial cells. HaCaT-keratinocytes were exposed to different doses of acrolein and whole phase CS using a unique smoking simulator apparatus that mimics the exposure in smokers. The rate of intracellular protein carbonyl modification was examined 10-60 min after the exposure by Western blot. In addition, the effect of pre-incubation with a thiol scavenger N-acetylcysteine (NAC) was also assessed. We found that intracellular protein carbonyls increased as fast as 10 min after CS exposure and their concentration doubled after 20 min, with a slight elevation afterwards. Also, carbonyl levels increased gradually as CS and acrolein doses were elevated. Addition of 1 mM NAC neutralized part of the damage. We conclude that CS and acrolein intracellular protein carbonylation is dose- and time- dependent. Even a short time exposure to CS and its aldehydic constituents can be potentially harmful.

  2. Acrolein impairs ATP binding cassette transporter A1-dependent cholesterol export from cells through site-specific modification of apolipoprotein A-I.

    PubMed

    Shao, Baohai; Fu, Xiaoyun; McDonald, Thomas O; Green, Pattie S; Uchida, Koji; O'Brien, Kevin D; Oram, John F; Heinecke, Jay W

    2005-10-28

    Acrolein is a highly reactive alpha,beta-unsaturated aldehyde, but the factors that control its reactions with nucleophilic groups on proteins remain poorly understood. Lipid peroxidation and threonine oxidation by myeloperoxidase are potential sources of acrolein during inflammation. Because both pathways are implicated in atherogenesis and high density lipoprotein (HDL) is anti-atherogenic, we investigated the possibility that acrolein might target the major protein of HDL, apolipoprotein A-I (apoA-I), for modification. Tandem mass spectrometric analysis demonstrated that lysine 226, located near the center of helix 10 in apoA-I, was the major site modified by acrolein. Importantly, this region plays a critical role in the cellular interactions and ability of apoA-I to transport lipid. Indeed, we found that conversion of Lys-226 to N(epsilon)-(3-methylpyridinium)lysine by acrolein associated quantitatively with decreased cholesterol efflux from cells via the ATP-binding cassette transporter A1 pathway. In the crystal structure of truncated apoA-I, Glu-234 lies adjacent to Lys-226, suggesting that negatively charged residues might direct the modification of specific lysine residues in proteins. Finally, immunohistochemical studies with a monoclonal antibody revealed co-localization of apoA-I with acrolein adducts in human atherosclerotic lesions. Our observations suggest that acrolein might interfere with normal reverse cholesterol transport by HDL by modifying specific sites in apoA-I. Thus, acrolein might contribute to atherogenesis by impairing cholesterol removal from the artery wall. PMID:16126721

  3. Acrolein, an α,β-unsaturated aldehyde, irreversibly inhibits the acetylation of aromatic amine xenobiotics by human arylamine N-acetyltransferase 1.

    PubMed

    Bui, Linh C; Manaa, Amine; Xu, Ximing; Duval, Romain; Busi, Florent; Dupret, Jean-Marie; Rodrigues-Lima, Fernando; Dairou, Julien

    2013-07-01

    Acrolein is an electrophilic α,β-unsaturated aldehyde of industrial, pharmaceutic, and toxicologic importance to which we are exposed in environmental, occupational, and therapeutic situations. Acrolein is known to exert different biologic effects through reactions with cellular macromolecules such as DNA, certain proteins, or glutathione. In many situations (such as in tobacco smoke or other fumes), exposure to acrolein occurs concomitantly with other compounds such as aromatic amine chemicals. Interestingly, it has been shown that acrolein could impact the cellular metabolism of aromatic xenobiotics through an indirect mechanism based on the transcriptional induction of phase II xenobiotic-metabolizing enzymes. Here we report a novel mechanism by which acrolein acts on the metabolism of aromatic foreign chemicals. We provide molecular, kinetic, and cellular evidence that acrolein can react directly and irreversibly with arylamine N-acetyltransferases, a major family of xenobiotic-metabolizing enzymes involved in the metabolization of aromatic amine chemicals. Formation of an acrolein adduct with a catalytic cysteine residue in the active site is responsible for the impairment of aromatic amine acetylation by the enzyme. This biochemical process may represent an additional mechanism by which acrolein impacts the metabolism and fate of aromatic amine drugs and pollutants.

  4. Methanol from coal

    NASA Technical Reports Server (NTRS)

    Miller, D. R.

    1978-01-01

    Economic feasibility of methanol or methyl fuel produced from coal using existing technology is discussed. Other factors considered include environmental, safety, toxicity, transportation, so storage, ease of burning, and retrofitting of present boilers. Demonstrations of its uses as a boiler fuel and as a turbine fuel are cited.

  5. Sources and seasonality of atmospheric methanol based on tall tower measurements in the US Upper Midwest

    NASA Astrophysics Data System (ADS)

    Hu, L.; Mohr, M.; Wells, K. C.; Griffis, T. J.; Helmig, D.; Millet, D. B.

    2011-12-01

    Methanol (CH3OH) plays an important role in the atmosphere as a source of carbon monoxide (CO) and formaldehyde (HCHO), however the magnitude and distribution of methanol emissions remain poorly constrained. Here we present over one year of continuous atmospheric methanol measurements from the University of Minnesota tall tower Trace Gas Observatory (KCMP tall tower; 185 m a.g.l.), and interpret the dataset in terms of constraints on regional methanol sources and seasonality. The seasonal cycle of methanol concentrations observed at the KCMP tall tower is generally similar to that simulated by a global 3-D chemical transport model (GEOS-Chem, driven with MEGANv2.0 biogenic emissions) except the seasonal peak occurs ~1 month earlier in the observations, apparently reflecting a model underestimate of emission rates for younger versus older leaves. Based on a source tracer approach, which we evaluate using GEOS-Chem and with multiple tracers, we estimate that anthropogenic emissions account for approximately 40% of ambient methanol abundance during winter and 10% during summer. During daytime in summer, methanol concentrations increase exponentially with temperature, reflecting the temperature sensitivity of the biogenic source, and the observed temperature dependence is statistically consistent with that in the model. Nevertheless, summertime concentrations are underestimated by on average 35% in the model for this region. The seasonal importance of methanol as a source of HCHO and CO is highest in spring through early summer, when biogenic methanol emissions are high but isoprene emissions are still relatively low. During that time observed methanol concentrations account for on average 20% of the total CO and HCHO production rates as simulated by GEOS-Chem, compared to 12% later in the summer and 12% on an annual average basis. The biased seasonality in the model means that the photochemical role for methanol early in the growing season is presently underestimated.

  6. The dimers of glyoxal and acrolein with H 2O and HF: Negative intramolecular coupling and blue-shifted C-H stretch

    NASA Astrophysics Data System (ADS)

    Karpfen, Alfred; Kryachko, Eugene S.

    2010-04-01

    The structures and the vibrational spectra of the hydrogen-bonded complexes: glyoxal-H 2O, glyoxal-HF, acrolein-H 2O, and acrolein-HF, are investigated within the MP2/aug-cc-pVTZ computational approach. It is demonstrated that the calculated blue shifts of the C-H stretching frequencies in the glyoxal-H 2O complexes are only indirectly pertinent to hydrogen bonding to the C-H group. The comparison with the glyoxal-HF and the acrolein-HF complexes reveals that these blue shifts are a direct consequence of a negative intramolecular coupling between vicinal C dbnd O and C-H bonds in the aldehyde groups of isolated glyoxal and acrolein molecules. To support this interpretation, the halogen-bonded complexes glyoxal-BrF and acrolein-BrF are discussed.

  7. Methanol/sorbitol co-feeding induction enhanced porcine interferon-α production by P. pastoris associated with energy metabolism shift.

    PubMed

    Gao, Min-Jie; Li, Zhen; Yu, Rui-Song; Wu, Jian-Rong; Zheng, Zhi-Yong; Shi, Zhong-Ping; Zhan, Xiao-Bei; Lin, Chi-Chung

    2012-09-01

    The production of porcine interferon-α (pIFN-α) by Pichia pastoris was largely enhanced when adopting sorbitol/methanol co-feeding induction strategy at 30 °C in a 10-L fermentor. Analysis of energy regeneration pattern and carbon metabolism revealed that major energy metabolism energizing pIFN-α synthesis shifted from formaldehyde dissimilatory energy metabolism pathway to TCA cycle under the methanol/sorbitol co-feeding induction strategy. The sorbitol/methanol co-feeding induction strategy weakened formaldehyde dissimilatory pathway and repressed the accumulation of toxic metabolite-formaldehyde, reduced theoretical oxygen consumption rate and oxygen supply requirement, and increased energy/methanol utilization efficiency so that more methanol could be effectively used for pIFN-α synthesis. As a result, pIFN-α antiviral activity reached a highest level of 1.8 × 10(7) IU/mL which was about 10- to 200-folds of those obtained under pure methanol induction at 20 and 30 °C, respectively.

  8. Toxicity and biodegradation of formaldehyde in anaerobic methanogenic culture.

    PubMed

    Qu, M; Bhattacharya, S K

    1997-09-01

    Formaldehyde is present in several industrial wastewaters including petrochemical wastes. In this study, the toxicity and degradability of formaldehyde in anaerobic systems were investigated. Formaldehyde showed severe toxicity to an acetate enrichment methanogenic culture. As low as 10 mg/L (0.33 mM) of formaldehyde in the reactor completely inhibited acetate utilization. Formaldehyde, however, was degraded while acetate utilization was inhibited. Degradation of formaldehyde (Initial concentration < or =30 mg/L) followed Monod model with a rate constant, k, of 0.35-0.46 d(-1). At higher initial concentrations (> or =60 mg/L), formaldehyde degradation was inhibited and partial degradation was possible. The initial formaldehyde to biomass ratio, S(0)/X(0), was useful to predict the degradation potential of high formaldehyde concentrations in batch systems. When S(0)/X(0) < or = 0.1, formaldehyde was completely degraded with initial concentration of up to 95 mg/L; when S(0)/X(0) > or = 0.29, formaldehyde at higher than 60 mg/L was only partially degraded. The inhibition of formaldehyde degradation in batch systems could be avoided by repeated additions of low concentrations of formaldehyde (up to 30 mg/L). Chemostats (14-day retention time) showed degradation of 74 mg/L-d (1110 mg/L) of influent formaldehyde with a removal capacity of 164 mg/g VSS-day. A spike of 30 mg/L (final concentration in the chemostat) formaldehyde to the chemostat caused only a small increase in effluent acetate concentration for 3 days. But a spike of 60 mg/L (final concentration in the chemostat) formaldehyde to the chemostat resulted in a dramatic increase in acetate concentration in the effluent. The results also showed that the acetate enrichment culture was not acclimated to formaldehyde even after 226 days. (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 55: 727-736, 1997.

  9. Hydralazine inhibits rapid acrolein-induced protein oligomerization: role of aldehyde scavenging and adduct trapping in cross-link blocking and cytoprotection.

    PubMed

    Burcham, Philip C; Pyke, Simon M

    2006-03-01

    Hydralazine strongly suppresses the toxicity of acrolein, a reactive aldehyde that contributes to numerous health disorders. At least two mechanisms may underlie the cytoprotection, both of which involve the nucleophilic hydrazine possessed by hydralazine. Under the simplest scenario, hydralazine directly scavenges free acrolein, decreasing intracellular acrolein availability and thereby suppressing macromolecular adduction. In a second "adduct-trapping" mechanism, the drug forms hydrazones with acrolein-derived Michael adducts in cell proteins, preventing secondary reactions of adducted proteins that may trigger cell death. To identify the most important mechanism, we explored these two pathways in mouse hepatocytes poisoned with the acrolein precursor allyl alcohol. Intense concentration-dependent adduct-trapping in cell proteins accompanied the suppression of toxicity by hydralazine. However, protective concentrations of hydralazine did not alter extracellular free acrolein levels, cellular glutathione loss, or protein carbonylation, suggesting that the cytoprotection is not due to minimization of intracellular acrolein availability. To explore ways whereby adduct-trapping might confer cytoprotection, the effect of hydralazine on acrolein-induced protein cross-linking was examined. Using bovine pancreas ribonuclease A as a model protein, acrolein caused rapid time- and concentration-dependent cross-linking, with dimerized protein detectable within 45 min of commencing protein modification. Lysine adduction in monomeric protein preceded the appearance of oligomers, whereas reductive methylation of protein amine groups abolished both adduction and oligomerization. Hydralazine inhibited cross-linking if added 30 min after commencing acrolein exposure but was ineffective if added after a 90-min delay. Adduct-trapping closely accompanied the inhibition of cross-linking by hydralazine. These findings suggest that cross-link blocking may contribute to hydralazine

  10. Formaldehyde exposure and health status in households.

    PubMed Central

    Broder, I; Corey, P; Brasher, P; Lipa, M; Cole, P

    1991-01-01

    This report describes a case study concerned with acute and subacute health effects of formaldehyde in the indoor air, which is based on a large group of control houses and houses retroinsulated 4 to 5 years earlier with urea formaldehyde foam insulation (UFFI). Both groups underwent an environmental and health assessment on two occasions separated by an interval of 12 months, during which about one-half of the UFFI group performed remedial work on their houses. The results show that in the first survey of the study population, before remedial work, there was a moderate excess of many adverse health status indicators among the UFFI subset relative to the controls. This was associated with the presence of direct exposure-response relationships between formaldehyde levels in the UFFI houses and the prevalence of a number of symptoms. No comparable relationships were seen among the controls. At the second survey, performed following the removal of the UFFI, there was an appreciable reduction in the excess of most adverse health status indicators among the UFFI subjects. This improvement in health status among the UFFI removal subset was not associated with any significant diminution of formaldehyde exposures, although the previously observed exposure-response relationships had vanished. These observations imply that the findings obtained in the preremedial stage of the study cannot be explained by formaldehyde exposure alone. PMID:1821362

  11. Tissue sensitivity of the rat upper and lower extrapulmonary airways to the inhaled electrophilic air pollutants diacetyl and acrolein.

    PubMed

    Cichocki, Joseph A; Smith, Gregory J; Morris, John B

    2014-11-01

    The target site for inhaled vapor-induced injury often differs in mouth-breathing humans compared with nose-breathing rats, thus complicating the use of rat inhalation toxicity data for assessment of human risk. We sought to examine sensitivity of respiratory/transitional nasal (RTM) and tracheobronchial (TBM) mucosa to two electrophilic irritant vapors: diacetyl and acrolein. Computational fluid dynamic physiologically based pharmacokinetic modeling was coupled with biomarker assessment to establish delivered dose-response relationships in RTM and TBM in male F344 rats following 6 h exposure to diacetyl or acrolein. Biomarkers included glutathione status, proinflammatory and antioxidant gene mRNA levels, and nuclear translocation of nuclear factor (erythroid-derived 2)-like 2 (Nrf2). Modeling revealed that 0.0094-0.1653 μg acrolein/min-cm(2) and 3.9-21.6 μg diacetyl/min-cm(2) were deposited into RTM/TBM. Results indicate RTM and TBM were generally of similar sensitivity to diacetyl and acrolein. For instance, both tissues displayed induction of antioxidant and proinflammatory genes, and nuclear accumulation of Nrf2 after electrophile exposure. Hierarchical cellular response patterns were similar in RTM and TBM but differed between vapors. Specifically, diacetyl exposure induced proinflammatory and antioxidant genes concomitantly at low exposure levels, whereas acrolein induced antioxidant genes at much lower exposure levels than that required to induce proinflammatory genes. Generally, diacetyl was less potent than acrolein, as measured by maximal induction of transcripts. In conclusion, the upper and lower extrapulmonary airways are of similar sensitivity to inhaled electrophilic vapors. Dosimetrically based extrapolation of nasal responses in nose-breathing rodents may provide an approach to predict risk to the lower airways of humans during mouth-breathing.

  12. Investigation of the reactions of small neutral iron oxide clusters with methanol

    NASA Astrophysics Data System (ADS)

    Xie, Yan; Dong, Feng; Heinbuch, Scott; Rocca, Jorge J.; Bernstein, Elliot R.

    2009-03-01

    Reactions of neutral iron oxide clusters (FemOn, m =1-2, n =0-5) with methanol (CH3OH) in a fast flow reactor are investigated by time of flight mass spectrometry. Detection of the neutral iron oxide cluster distribution and reaction intermediates and products is accomplished through single photon ionization by a 118 nm (10.5 eV) VUV laser. Partially deuterated methanol (CD3OH) is employed to distinguish reaction products and reaction mechanisms. Three major reactions are identified experimentally: CH3OH association with FeO; methanol dehydrogenation on FeO1,2 and Fe2O2-5; and (CH2O)Fe formation. Density functional theory calculations are carried out to identify reaction products, and to explore the geometric and electronic structures of the iron oxide clusters, reaction intermediates, and transition states, and to evaluate reaction pathways. Neutral formaldehyde is calculated to be formed on FeO1,2 and Fe2O2-5 clusters. Hydrogen transfer from methanol to iron oxide clusters occurs first from the O-H moiety of methanol, and is followed by a hydrogen transfer from the C-H moiety of methanol. Computational results are in good agreement with experimental observations and reveal reaction mechanisms for neutral iron oxide clusters taking methanol to formaldehyde through various reaction intermediates. Based on the experimental results and the calculated reaction mechanisms and pathways, complete catalytic cycles are suggested for the heterogeneous reaction of CH3OH to CH2O facilitated by an iron oxide catalyst.

  13. Proton conducting polymer electrolytes based on phosphorylated phenol-formaldehyde resins

    NASA Astrophysics Data System (ADS)

    Kędzierski, Michał; Florjańczyk, Zbigniew

    Phosphorylated phenol-formaldehyde (PPF) resins were synthesized and investigated as the acidic components of proton conducting polymer electrolytes. The synthesis of PPF resins was carried out by melt polycondensation of monophenyl phosphate and formaldehyde (in the form of trioxane). The structure and molecular weight characterization of PPF resins were performed employing 1H-, 13C- and 31P-NMR spectroscopy, Fast Atom Bombardment mass spectrometry and elemental analysis. PPF resins may be cured with an excess of formaldehyde. Depending on the curing conditions, products of different crosslinking density (expressed by equilibrium swelling ratio) and total ion-exchange capacity up to 9 mequiv. g -1 may be obtained. The soluble and crosslinked PPF resins were examined from the viewpoint of conducting properties and hydrolytical stability. Crosslinked PPF resins embedded in poly(vinylidene fluoride) binder form ion-exchange membranes of ambient conductivities above 0.05 S cm -1. These composite membranes have been investigated in a methanol fuel cell and showed stable performance during several hours of cell operation.

  14. Tropospheric methanol observations from space: constraints on the seasonality of biogenic emissions

    NASA Astrophysics Data System (ADS)

    Wells, K. C.; Millet, D. B.; Cady-Pereira, K. E.; Shephard, M. W.; Xiao, Y.; Razavi, A.; Clerbaux, C.

    2011-12-01

    Methanol is the most abundant non-methane organic compound in the atmosphere, and is an important precursor of atmospheric pollutants such as CO and formaldehyde. The recent development of methanol retrievals from nadir-viewing satellite-based platforms offers powerful new information for quantifying methanol emissions on a global scale. This study uses methanol observations from the Tropospheric Emission Spectrometer (TES) on the Aura satellite and the Infrared Atmospheric Sounding Interferometer (IASI) on the MetOp-A satellite, in conjunction with aircraft data, to investigate methanol emissions from major plant functional types in the GEOS-Chem global chemical transport model (driven with MEGAN biogenic emissions). We first evaluate the TES methanol retrievals by comparing to simulation results and flight observations from several North American field campaigns. Results show that the retrieval performs well when the degrees of freedom for signal are above 0.5. We analyze one full year of TES and IASI observations and find a persistent model underestimate in springtime, and make recommendations for an improved seasonal distribution of biogenic methanol emissions over temperate regions of the globe.

  15. Convenient quantification of methanol concentration detection utilizing an integrated microfluidic chip

    PubMed Central

    Wang, Yao-Nan; Yang, Ruey-Jen; Ju, Wei-Jhong; Wu, Ming-Chang; Fu, Lung-Ming

    2012-01-01

    A rapid and simple technique is proposed for methanol concentration detection using a PMMA (Polymethyl-Methacrylate) microfluidic chip patterned using a commercially available CO2 laser scriber. In the proposed device, methanol and methanol oxidase (MOX) are injected into a three-dimensional circular chamber and are mixed via a vortex stirring effect. The mixture is heated to prompt the formation of formaldehyde and is flowed into a rectangular chamber, to which fuchsin-sulphurous acid is then added. Finally, the microchip is transferred to a UV spectrophotometer for methanol detection purposes. The experimental results show that a correlation coefficient of R2 = 0.9940 is obtained when plotting the optical density against the methanol concentration for samples and an accuracy as high as 93.1% are compared with the determined by the high quality gas chromatography with concentrations in the range of 2 ∼ 100 ppm. The methanol concentrations of four commercial red wines are successfully detected using the developed device. Overall, the results show that the proposed device provides a rapid and accurate means of detecting the methanol concentration for a variety of applications in the alcoholic beverage inspection and control field. PMID:23940501

  16. Formaldehyde content of atmospheric aerosol.

    PubMed

    Toda, Kei; Yunoki, Satoru; Yanaga, Akira; Takeuchi, Masaki; Ohira, Shin-Ichi; Dasgupta, Purnendu K

    2014-06-17

    Formaldehyde (HCHO) is a highly soluble polar molecule with a large sticking coefficient and thus likely exists in both gaseous and particulate forms. Few studies, however, address particulate HCHO (HCHO(p)). Some report that HCHO(p) concentrations (obtained only with long duration sampling) are very low. The lack of data partly reflects the difficulty of specifically measuring HCHO(p). Long duration filter sampling may not produce meaningful results for a variety of reasons. In this work, gaseous HCHO (HCHO(g)) and (HCHO(p)) were, respectively, collected with a parallel plate wet denuder (PPWD) followed by a mist chamber/hydrophilic filter particle collector (PC). The PPWD quantitatively removed HCHO(g) and the PC then collected the transmitted aerosol. The collected HCHO from either device was alternately analyzed by Hantzsch reaction-based continuous flow fluorometry. Each gas and particle phase measurement took 5 min each, with a 10 min cycle. The limits of detection were 0.048 and 0.0033 μg m(-3), respectively, for HCHO(g) and HCHO(p). The instrument was deployed in three separate campaigns in a forest station in western Japan in March, May, and July of 2013. Based on 1296 data pairs, HCHO(p), was on the average, 5% of the total HCHO. Strong diurnal patterns were observed, with the HCHO(p) fraction peaking in the morning. The relative humidity dependence of the partition strongly suggests that it is driven by the liquid water content of the aerosol phase. However, HCHO(p) was 100× greater than that expected from Henry's law. We propose that the low water activity in the highly saline droplets lead to HCHO oligomerization.

  17. 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.

  18. Acrolein Exposure in U.S. Tobacco Smokers and Non-Tobacco Users: NHANES 2005–2006

    PubMed Central

    deCastro, B. Rey; Morrow, John C.; Blount, Benjamin C.

    2015-01-01

    Background Acrolein is a highly reactive α,β unsaturated aldehyde and respiratory irritant. Acrolein is formed during combustion (e.g., burning tobacco or biomass), during high-temperature cooking of foods, and in vivo as a product of oxidative stress and polyamine metabolism. No biomonitoring reference data have been reported to characterize acrolein exposure for the U.S. population. Objectives Our goals were to a) evaluate two acrolein metabolites in urine—N-acetyl-S-(3-hydroxypropyl)-l-cysteine (3HPMA) and N-acetyl-S-(2-carboxyethyl)-l-cysteine (CEMA)—as biomarkers of exposure to acrolein for the U.S. population by age, sex, race, and smoking status; and b) assess tobacco smoke as a predictor of acrolein exposure. Methods We analyzed urine from National Health and Nutrition Examination Survey (NHANES 2005–2006) participants ≥ 12 years old (n = 2,866) for 3HPMA and CEMA using ultra-high-performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry (UPLC/ESI-MSMS). Sample-weighted linear regression models stratified for non-tobacco users versus tobacco smokers (as defined by serum cotinine and self-report) characterized the association of urinary 3HPMA and CEMA with tobacco smoke exposure, adjusting for urinary creatinine, sex, age, and race/ethnicity. Results 3HPMA and CEMA levels were higher among tobacco smokers (cigarettes, cigars, and pipe users) than among non-tobacco users. The median 3HPMA levels for tobacco smokers and non-tobacco users were 1,089 and 219 μg/g creatinine, respectively. Similarly, median CEMA levels were 203 μg/g creatinine for tobacco smokers and 78.8 μg/g creatinine for non-tobacco users. Regression analysis showed that serum cotinine was a significant positive predictor (p < 0.0001) of both 3HPMA and CEMA among tobacco smokers. Conclusions Tobacco smoke was a significant predictor of acrolein exposure in the U.S. population. Citation Alwis KU, deCastro BR, Morrow JC, Blount BC. 2015

  19. Production of Melamine-Formaldehyde PCM Microcapsules with Ammonia Scavenger used for Residual Formaldehyde Reduction.

    PubMed

    Sumiga, Boštjan; Knez, Emil; Vrtačnik, Margareta; Ferk-Savec, Vesna; Starešinič, Marica; Boh, Bojana

    2011-03-01

    Paraffinic phase change materials (PCM) were microencapsulated by in situ polymerization of melamine-formaldehyde prepolymers. Partly methylated trimethylolmelamine was used as an aminoaldehyde prepolymer for the microcapsule wall, a styrene-maleic acid anhydride copolymer as an emulsifier and modifying agent, and ammonia as a scavenger for reducing residual formaldehyde. For the determination of residual formaldehyde in a ppm concentration range, EDANA and malachite green analytical methods were studied, and the EDANA 210.1-99 was applied for the determination of residual formaldehyde in 25 samples of microcapsules, produced in a 200-L reactor. A linear correlation was observed between the added ammonia scavenger concentration and the reduction of residual formaldehyde concentration. Compared with 0.45% (4500 ppm) formaldehyde in a non-treated microcapsule suspension, with ammonia scavenger concentrations 0.80, 0.90 and 1.35%, the concentration of residual formaldehyde dropped to 0.27, 0.20 and 0.09% (i.e. 2700, 2000 and 900 ppm), respectively. Morphological characterisation of microcapsules by SEM and microcapsule wall permeability measurements by gravimetry / mass loss at an elevated temperature (135 °C) suggested that ammonia positively contributed to the wall elasticity / durability, while microcapsules with no ammonia scavenger added tended to have more brittle walls, and were more prone to cracking.

  20. Hydroxytyrosol protects retinal pigment epithelial cells from acrolein-induced oxidative stress and mitochondrial dysfunction

    PubMed Central

    Liu, Zhongbo; Sun, Lijuan; Zhu, Lu; Jia, Xu; Li, Xuesen; Jia, Haiqun; Wang, Ying; Weber, Peter; Long, Jiangang; Liu, Jiankang

    2008-01-01

    Hydroxytyrosol (HTS) is a natural polyphenol abundant in olive oil. Increasing evidence indicates HTS has beneficial effect on human health for preventing various diseases. In the present study, we investigated the protective effects of HTS on acrolein-induced toxicity in human retinal pigment epithelial cell line, ARPE-19, a cellular model of smoking- and age-related macular degeneration. Acrolein, a major component of the gas phase cigarette smoke and also a product of lipid peroxidation in vivo, at 75 µmol/L for 24 h caused significant loss of cell viability, oxidative damage (increase in oxidant generation and oxidative damage to proteins and DNA, decrease in antioxidants and antioxidant enzymes, and also inactivation of the Keap1/Nrf2 pathway), and mitochon-drial dysfunction (decrease in membrane potential, activities of mitochondrial complexes, viable mitochondria, oxygen consumption, and factors for mitochondrial biogenesis, and increase in calcium). Pre-treatment with HTS dose dependently and also time dependently protected the ARPE-19 cells from acrolein-induced oxidative damage and mitochondrial dysfunction. A short-term pre-treatment with HTS (48 h) required >75 µmol/L for showing protection while a long-term pre-treatment (7 days) showed protective effect from 5 µmol/L on. The protective effect of HTS in this model was as potent as that of established mitochondria-targeting antioxidant nutrients. These results suggest that HTS is also a mitochondrial-targeting antioxidant nutrient and that dietary administration of HTS may be an effective measure in reducing and or preventing cigarette smoke-induced or age-related retinal pigment epithelial degeneration, such as age-associated macular degeneration. PMID:20938484

  1. Isomer specific product detection in the reaction of CH with acrolein.

    PubMed

    Lockyear, Jessica F; Welz, Oliver; Savee, John D; Goulay, Fabien; Trevitt, Adam J; Taatjes, Craig A; Osborn, David L; Leone, Stephen R

    2013-10-31

    The products formed in the reaction between the methylidene radical (CH) and acrolein (CH2═CHCHO) are probed at 4 Torr and 298 K employing tunable vacuum-ultraviolet synchrotron light and multiplexed photoionization mass-spectrometry. The data suggest a principal exit channel of H loss from the adduct to yield C4H4O, accounting for (78 ± 10)% of the products. Examination of the photoionization spectra measured upon reaction of both CH and CD with acrolein reveals that the isomeric composition of the C4H4O product is (60 ± 12)% 1,3-butadienal and (17 ± 10)% furan. The remaining 23% of the possible C4H4O products cannot be accurately distinguished without more reliable photoionization spectra of the possible product isomers but most likely involves oxygenated butyne species. In addition, C2H2O and C3H4 are detected, which account for (14 ± 10)% and (8 +10, -8)% of the products, respectively. The C2H2O photoionization spectrum matches that of ketene and the C3H4 signal is composed of (24 ± 14)% allene and (76 ± 22)% propyne, with an upper limit of 8% placed on the cyclopropene contribution. The reactive potential energy surface is also investigated computationally, and specific rate coefficients are calculated with RRKM theory. These calculations predict overall branching fractions for 1,3-butadienal and furan of 27% and 12%, respectively, in agreement with the experimental results. In contrast, the calculations predict a prominent CO + 2-methylvinyl product channel that is at most a minor channel according to the experimental results. Studies with the CD radical strongly suggest that the title reaction proceeds predominantly via cycloaddition of the radical onto the C═O bond of acrolein, with cycloaddition to the C═C bond being the second most probable reactive mechanism.

  2. Eucomic acid methanol monosolvate

    PubMed Central

    Li, Guo-Qiang; Li, Yao-Lan; Wang, Guo-Cai; Liang, Zhi-Hong; Jiang, Ren-Wang

    2011-01-01

    In the crystal structure of the title compound [systematic name: 2-hy­droxy-2-(4-hy­droxy­benz­yl)butane­dioic acid methanol monosolvate], C11H12O6·CH3OH, the dihedral angles between the planes of the carboxyl groups and the benzene ring are 51.23 (9) and 87.97 (9)°. Inter­molecular O—H⋯O hydrogen-bonding inter­actions involving the hy­droxy and carb­oxy­lic acid groups and the methanol solvent mol­ecule give a three-dimensional structure. PMID:22091200

  3. Exposure to formaldehyde: effects of pulmonary function

    SciTech Connect

    Alexandersson, R.; Kolmodin-Hedman, B.; Hedenstierna, G.

    1982-09-01

    Forty-seven subjects exposed to formaldehyde (mean air concentration 0.45 mg/m/sup 3/) and 20 unexposed subjects, all of whom were employed at a carpentry shop, were studied with regard to symptoms and pulmonary function. Symptoms involving eyes and throat as well as chest oppression were significantly more common in the exposed subjects than in the unexposed controls. Spirometry and single breath nitrogen washout were normal Monday morning before exposure to formaldehyde. A reduction in forced expiratory volume in 1 sec by an average of 0.2 L (P = .002), percent forced expiratory volume by 2% (P = .04), maximum midexpiratory flow by 0.3 L/sec (P = .04) and an increase in closing volume in percentage of vital capacity by 3.4% (P = .002) were seen after a day of work and exposure to formaldehyde, suggesting bronchoconstriction. Smokers and nonsmokers displayed similar changes in spirometry and nitrogen washout.

  4. Metabolism and binding of cyclophosphamide and its metabolite acrolein to rat hepatic microsomal cytochrome P-450

    SciTech Connect

    Marinello, A.J.; Bansal, S.K.; Paul, B.; Koser, P.L.; Love, J.; Struck, R.F.; Gurtoo, H.L.

    1984-10-01

    The hepatic cytochrome P-450-mediated metabolism and metabolic activation of (chloroethyl-3H)cyclophosphamide (( chloroethyl-3H)CP) and (4-14C)cyclophosphamide (( 4-14C)CP) were investigated in vitro in the reconstituted system containing cytochrome P-450 isolated from phenobarbital-treated rats. In addition, hepatic microsomal binding and the hepatic microsome-mediated metabolism of (14C)acrolein, a metabolite of (4-14C)CP, were also investigated. The metabolism of (chloroethyl-3H)CP and (4-14C)CP to polar metabolites was found to depend on the presence of NADPH and showed concentration dependence with respect to cytochrome P-450 and NADPH:cytochrome P-450 reductase. Km and Vmax values were essentially similar. The patterns of inhibition by microsomal mixed-function oxidase inhibitors, anti-cytochrome P-450 antibody, and heat denaturation of the cytochrome P-450 were essentially similar, with subtle differences between (4-14C)CP and (chloroethyl-3H)CP metabolism. The in vitro metabolic activation of CP in the reconstituted system demonstrated predominant binding of (chloroethyl-3H)CP to nucleic acids and almost exclusive binding of (4-14C)CP to proteins. Gel electrophoresis-fluorography of the proteins in the reconstituted system treated with (4-14C)CP demonstrated localization of the 14C label in the cytochrome P-450 region. To examine this association further, hepatic microsomes were modified with (14C)acrolein in the presence and the absence of NADPH. The results confirmed covalent association between (14C)acrolein and cytochrome P-450 in the microsomes and also demonstrated further metabolism of (14C)acrolein, apparently to an epoxide, which is capable of binding covalently to proteins. The results of these investigations not only confirm the significance of primary metabolism but also emphasize the potential role of the secondary metabolism of cyclophosphamide in some of its toxic manifestations.

  5. Surface component distribution in a vanadium-molybdenum oxide catalyst for making acrylic acid from acrolein

    SciTech Connect

    Zazhigalov, V.A.; Kholyavenko, K.M.

    1986-11-01

    A scanning electron microscope and microprobe analyzer have been used to examine the surfaces of vanadium-molybdenum catalysts on aerosil. It is found that the phase VMo/sub 3/O/sub 11/ is formed, which is dispersed on the SiO/sub 2/. MoO/sub 3/ crystals of various shapes occur at the surface of the dispersed phase. It is suggested that this catalyst is highly active in oxidizing acrolein to acrylic acid because of the presence of VMo/sub 3/O/sub 11/.

  6. Determination of acrolein in serum by high-performance liquid chromatography with fluorescence detection after pre-column fluorogenic derivatization using 1,2-diamino-4,5-dimethoxybenzene.

    PubMed

    Imazato, Takahiro; Kanematsu, Mariko; Kishikawa, Naoya; Ohyama, Kaname; Hino, Takako; Ueki, Yukitaka; Maehata, Eisuke; Kuroda, Naotaka

    2015-09-01

    Acrolein is a major unsaturated aldehyde that is generated during the lipid peroxidation process. The measurement of acrolein in biological samples should be useful to estimate the degree of lipid peroxidation and to evaluate the effect of hazardous properties of acrolein on human health. In this study, a highly sensitive and selective high-performance liquid chromatography with fluorescence detection method was developed for the determination of acrolein in human serum. The proposed method involves the pre-column fluorogenic derivatization of acrolein with 1,2-diamino-4,5-dimethoxybenzene (DDB) as a reagent. The fluorescent derivative of acrolein could be detected clearly without any interfering reagent blank peaks because DDB does not have intrinsic fluorescence itself, and the detection limit was 10 nM (signal-to-noise ratio = 3). The proposed method could selectively detect acrolein in human serum with a simple protein precipitation treatment. PMID:25620324

  7. Determination of acrolein in serum by high-performance liquid chromatography with fluorescence detection after pre-column fluorogenic derivatization using 1,2-diamino-4,5-dimethoxybenzene.

    PubMed

    Imazato, Takahiro; Kanematsu, Mariko; Kishikawa, Naoya; Ohyama, Kaname; Hino, Takako; Ueki, Yukitaka; Maehata, Eisuke; Kuroda, Naotaka

    2015-09-01

    Acrolein is a major unsaturated aldehyde that is generated during the lipid peroxidation process. The measurement of acrolein in biological samples should be useful to estimate the degree of lipid peroxidation and to evaluate the effect of hazardous properties of acrolein on human health. In this study, a highly sensitive and selective high-performance liquid chromatography with fluorescence detection method was developed for the determination of acrolein in human serum. The proposed method involves the pre-column fluorogenic derivatization of acrolein with 1,2-diamino-4,5-dimethoxybenzene (DDB) as a reagent. The fluorescent derivative of acrolein could be detected clearly without any interfering reagent blank peaks because DDB does not have intrinsic fluorescence itself, and the detection limit was 10 nM (signal-to-noise ratio = 3). The proposed method could selectively detect acrolein in human serum with a simple protein precipitation treatment.

  8. The toxicity of methanol

    SciTech Connect

    Tephly, T.R. )

    1991-01-01

    Methanol toxicity in humans and monkeys is characterized by a latent period of many hours followed by a metabolic acidosis and ocular toxicity. This is not observed in most lower animals. The metabolic acidosis and blindness is apparently due to formic acid accumulation in humans and monkeys, a feature not seen in lower animals. The accumulation of formate is due to a deficiency in formate metabolism which is, in turn, related, in part, to low hepatic tetrahydrofolate (H{sub 4}folate). An excellent correlation between hepatic H{sub 4} folate and formate oxidation rates has been shown within and across species. Thus, humans and monkeys possess low hepatic H{sub 4}folate levels, low rates of formate oxidation and accumulation of formate after methanol. Formate, itself, produces blindness in monkeys in the absence of metabolic acidosis. In addition to low hepatic H{sub 4}folate concentrations, monkeys and humans also have low hepatic 10-formyl H{sub 4}folate dehydrogenase levels, the enzyme which is the ultimate catalyst for conversion of formate to carbon dioxide. This review presents the basis for the role of folic acid-dependent reactions in the regulation of methanol toxicity.

  9. California methanol assessment. Volume 2: Technical report

    NASA Technical Reports Server (NTRS)

    Otoole, R.; Dutzi, E.; Gershman, R.; Heft, R.; Kalema, W.; Maynard, D.

    1983-01-01

    Energy feedstock sources for methanol; methanol and other synfuels; transport, storage, and distribution; air quality impact of methanol use in vehicles, chemical methanol production and use; methanol utilization in vehicles; methanol utilization in stationary applications; and environmental and regulatory constraints are discussed.

  10. 24 CFR 3280.309 - Health Notice on formaldehyde emissions.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 24 Housing and Urban Development 5 2014-04-01 2014-04-01 false Health Notice on formaldehyde... Construction Requirements § 3280.309 Health Notice on formaldehyde emissions. (a) Each manufactured home shall have a Health Notice on formaldehyde emissions prominently displayed in a temporary manner in...

  11. The effect of clothing care activities on textile formaldehyde content.

    PubMed

    Novick, Rachel M; Nelson, Mindy L; McKinley, Meg A; Anderson, Grace L; Keenan, James J

    2013-01-01

    Textiles are commonly treated with formaldehyde-based residues that may potentially induce allergic contact dermatitis in sensitive individuals. This study examined the initial formaldehyde content in clothing and resulting changes due to care activities. Twenty clothing articles were examined and 17 of them did not have detectable levels of formaldehyde. One shirt contained a formaldehyde concentration of 3172 ppm, and two pairs of pants had formaldehyde concentrations of 1391 ppm and 86 ppm. The two highest results represent formaldehyde levels that are up to 40-fold greater than international textile regulations. The two items with the greatest formaldehyde content were washed and dried in a manner similar to that used by consumers, including hand and machine washing in hot or cold water followed by air or machine drying. The washing and drying procedures reduced formaldehyde levels to between 26 and 72% of untreated controls. Differences in the temperature or type of washing and drying did not result in a clear trend in the subsequent formaldehyde content. In addition, samples were hot ironed, which did not affect the formaldehyde content as significantly. Understanding the formaldehyde content in clothing and its potential reduction through care activities may be useful for manufacturers and formaldehyde-sensitive individuals.

  12. Developing a Reference Material for Formaldehyde Emissions Testing; Final Report

    EPA Science Inventory

    Exposure to formaldehyde has been shown to produce broad and potentially severe adverse human health effects. With ubiquitous formaldehyde sources in the indoor environment, formaldehyde concentrations in indoor air are usually higher than outdoors, ranging from 10 to 4000 μg/m3....

  13. Methanol oxidation on Fe2O3 catalysts and the effects of surface Mo.

    PubMed

    Bowker, M; Gibson, E K; Silverwood, I P; Brookes, C

    2016-07-01

    The adsorption of methanol on haematite has been investigated using temperature programmed methods, combined with in situ DRIFTS. Model catalysts based on this material have then been made with a shell-core configuration of molybdenum oxide monolayers on top of the haematite core. These are used as models of industrial iron molybdate catalysts, used to selectively oxidise methanol to formaldehyde, one of the major chemical outlets for methanol. Haematite itself is completely ineffective in this respect since it oxidises it to CO2 and the DRIFTS shows that this occurs by oxidation of methoxy to formate at around 200 °C. The decomposition behaviour is affected by the absence or presence of oxygen in the gas phase; oxygen destabilises the methoxy and enhances formate production. In contrast, when a monolayer of molybdena is placed onto the surface by incipient wetness, and it remains there after calcination, the pathway to formate production is blocked and formaldehyde is the main gas phase product in TPD after methanol dosing. PMID:27101412

  14. Chemical Characterization of Phenol/Formaldehyde Resins

    NASA Technical Reports Server (NTRS)

    Brayden, T. H.

    1986-01-01

    Report discusses tests of commercial phenol/formaldehyde resins to establish relationships among composition before use, behavior during curing, and strength after curing. Resin used in carbon/carbon laminates. In curing process, two molecules of phenol joined together in sequence of reactions involving molecule of formaldehyde. Last step of sequence, molecule of water released. Sequence repeats until one of ingredients used up, leaving solidified thermoset plastic. Issues to be resolved: number and relative abundances of ingredients, presence of certain chemical groups, heat-producing ability of resin, and range of molecular weights present.

  15. Effect of formaldehyde on cell proliferation and death.

    PubMed

    Szende, Béla; Tyihák, Erno

    2010-12-01

    Formaldehyde (HCHO) may reach living organisms as an exogenous agent or produced within cells. The so-called formaldehydogenic compounds like S-adenosyl-L-methionine, N-hydroxymethyl-L-arginine, 1'-methyl ascorbigen, methanol, E-N-trimethyl lysine and methylamine are special exogenous sources of HCHO. Endogenous HCHO can be formed from hydroxymethyl groups during enzymatic methylation and demethylation processes. HCHO, as a highly reactive compound, is considered to be involved in the induction of apoptosis, consequently in the pathogenesis of atherosclerosis and neurodegenerative processes. The biological action of HCHO is dose-dependent. In vitro studies on tumour cell and endothelial cell cultures showed that HCHO in the concentration of 10.0 mM caused necrotic cell death, 1.0 mM resulted in enhanced apoptosis and reduced mitotic activity, while 0.5 and 0.1 mM enhanced cell proliferation and reduced apoptotic activity. Among formaldehydogenic compounds N-hydroxymethyl-L-arginine, 1'-methyl ascorbigen and the HCHO donor resveratrol may be considered as potential inhibitors of cell proliferation. Endogenous HCHO in plants apparently play a role in regulation of apoptosis and cell proliferation. The genotoxic and carcinogentic effects of HCHO is due to production of DNA-protein cross-links. Low doses of HCHO, reducing apoptotic activity may also accumulate cells with such cross-links. Experimental data point to the possible therapeutic use of methylated lysine residues and methylated arginine residues in the case of neoplasms.

  16. Formation of a Vitamin C Conjugate of Acrolein and its Paraoxonase-mediated Conversion into 5,6,7,8-Tetrahydroxy-4-oxooctanal

    PubMed Central

    Kesinger, Nicholas G.; Langsdorf, Brandi L.; Yokochi, Alexandre F.; Miranda, Cristobal L.; Stevens, Jan F.

    2010-01-01

    Vitamin C (ascorbic acid) has been reported to participate in Michael addition reactions in vitro to form vitamin C conjugates with α,β-unsaturated aldehydes, such as acrolein. This study shows evidence for the formation and metabolism of the vitamin C conjugate of acrolein (AscACR) in cultured human monocytic THP-1 cells exposed to acrolein diacetate. By using 18O and 13C labeling in combination with liquid chromatography–tandem mass spectrometry, AscACR was shown to undergo hydrolytic conversion of the ascorbyl lactone into an intermediate carboxylic acid. Subsequent decarboxylation of the carboxylic acid yielded 5,6,7,8-tetrahydroxy-4-oxooctanal (THO). When THP-1 cells were pretreated with ascorbic acid (1 mM, 18 hours) and then exposed to acrolein diacetate, THO was detected as its pentafluorobenzyl oxime derivative in the cell lysates and medium. Treatment of THP-1 cells with both ascorbic acid and acrolein diacetate was required for THO formation. The formation of THO from AscACR was facilitated by the lactonase enzymes, human recombinant paraoxonases 1 and 2. THP-1 cells exhibited PON activity which explains the catalytic conversion of AscACR into THO in these cells. THO was formed in addition to metabolites of the glutathione conjugate of acrolein, indicating that THO formation contributes to the elimination of acrolein in a cellular environment. PMID:20353174

  17. Protective effects of caffeic acid and caffeic acid phenethyl ester against acrolein-induced neurotoxicity in HT22 mouse hippocampal cells.

    PubMed

    Huang, Yingjuan; Jin, Minghua; Pi, Rongbiao; Zhang, Junjie; Chen, Meihui; Ouyang, Ying; Liu, Anmin; Chao, Xiaojuan; Liu, Peiqing; Liu, Jun; Ramassamy, Charles; Qin, Jian

    2013-02-22

    Acrolein-induced oxidative stress is hypothesized to involve in the etiology of Alzheimer's disease (AD). Caffeic acid (CA) and caffeic acid phenethyl ester (CAPE) have antioxidative and neuroprotective properties. The present study investigated the protective effects of CA/CAPE on acrolein-induced oxidative neuronal toxicity. HT22 mouse hippocampal cells were pretreated with CA/CAPE and then exposed to acrolein. Cell viability, intracellular reactive oxygen species (ROS), and glutathione (GSH) level were measured. MAPKs and Akt/GSK3β signaling proteins as well as α/β-secretase of amyloid protein precursor were assayed by Western blotting. Pretreatment with CA/CAPE significantly attenuated acrolein-induced neurotoxicity, ROS accumulation, and GSH depletion. Further study suggested that CA/CAPE showed protective effects against acrolein by modulating MAPKs and Akt/GSK3β signaling pathways. Moreover, CA/CAPE restored the changes of β-secretase (BACE-1) and/or activation of α-secretase (ADAM-10) induced by acrolein. These findings suggest that CA/CAPE may provide a promising approach for the treatment of acrolein-related neurodegenerative diseases, such as AD.

  18. Methanol coupling in the zeolite chabazite studied via Car-Parrinello molecular dynamics

    NASA Astrophysics Data System (ADS)

    Lo, Cynthia; Giurumescu, Claudiu A.; Radhakrishnan, Ravi; Trout, Bernhardt L.

    We have used Car-Parrinello constrained molecular dynamics to study the coupling of two molecules of methanol in the zeolite chabazite to form ethanol and water. We have chosen to study this reaction because it represents the formation of the first C-C bond, which is thought to be the rate limiting step for the MTO and MTG processes. We have elucidated a new mechanism for this reaction that does not require the prior formation of surface methoxy groups or dimethyl ether intermediates. The mechanism involves stable intermediates of methane and protonated formaldehyde. We have also calculated an upper bound of the free energy barrier for the overall reaction, and found that it compares favourably with the rough experimental measurements available. Finally, we consider what are the natural reaction coordinates for the methanol-methanol coupling process.

  19. Effects of cyclophosphamide and acrolein in organoid cultures of mouse limb bud cells grown in the presence of adult rat hepatocytes.

    PubMed

    Ghaida, J; Merker, H J

    1992-01-01

    The effects were evaluated of cyclophosphamide (CPA) and its metabolite, acrolein, on chondrogenesis in organoid cultures of mouse limb bud mesenchymal cells co-cultured with non-enzymatically isolated adult rat hepatocytes. The studies were conducted with or without the simultaneous addition of 2-mercaptoethanesulphonic acid sodium (mesna) or glutathione (GSH). Alcian blue binding assay and light and electron microscopic techniques were used. Increasing concentrations of the two compounds (bioactivated CPA, 18-180 mum; acrolein, 50-500 mum) led to a dose-dependent inhibition of chondrogenesis associated with cellular dedifferentiation and/or cytotoxicity. Addition of mesna (1 mm) or GSH (1 mm) partially protected the cultures against CPA and acrolein. However, the protective effect depended on the dose of CPA or acrolein used. A higher protection was observed with mesna than with GSH, and the effect was more pronounced with acrolein than with CPA. The morphological findings suggested that CPA and acrolein acted by different mechanisms. Bioactivated CPA primarily inhibited the differentiation process, whereas acrolein exhibited a high cytotoxic activity affecting particularly monolayer cells that normally grow on the periphery of the cultures. These findings suggest that acrolein possesses a specific mode of action directed towards this type of cell. This could be explained by the specific shape and/or behaviour of the cells (i.e. cytoskeletal arrangement, proliferation rate, migration activity, intercellular communication pattern, etc.). The results demonstrated that the cell system used was suitable for the performance of cytotoxicity and teratogenicity studies such as those conducted with CPA and acrolein.

  20. [Formaldehyde in the environment and its effect on health].

    PubMed

    Kalinić, N

    1995-06-01

    The presence of formaldehyde in the environment is due to natural processes and to man-made sources. It is produced in large quantities and has varied applications. One of the most common uses is in urea-formaldehyde and melamine-formaldehyde resins. There are several indoor environmental sources that can result in human exposure including furniture containing formaldehyde-based resins, building materials, paints, disinfectants, carpets etc. Emphasis is placed on indoor formaldehyde levels and on the ways of their reduction or elimination.

  1. Unusual formaldehyde-induced hypersensitivity in two schoolgirls

    SciTech Connect

    Gammage, R.B. ); Hanna, W.T.; Painter, P.B. )

    1990-01-01

    Two schoolgirls developed a syndrome resembling Henoch-Schonlein purpura while attending a recently opened school insulated with urea-formaldehyde foam (UFFI). Skin rashes and swellings were accompanied by bizarre, blue-green discoloration of the skin. Subsequent investigations by county, state and federal authorities, and low measured concentrations of formaldehyde, prompted initial conclusions that in-school formaldehyde exposures were not responsible for the girls' problems. Subsequent controlled exposures to UFFI and formaldehyde while in hospital elicited the whole cascade of symptoms. The chronology of the onset and amplification of systems make it probable that the formaldehyde exposures precipitating the girls' hypersensitivity, occurred in the school. 3 refs.

  2. Dehydration of Glycerin to Acrolein Over Heteropolyacid Nano-Catalysts Supported on Silica-Alumina.

    PubMed

    Kang, Tae Hun; Choi, Jung Ho; Choi, Jun Seon; Song, In Kyu

    2015-10-01

    A series of H3PW12O40 nano-catalysts supported on silica-alumina (XH3PW12O40/SA (X = 10, 15, 20, 25, and 30)) with different H3PW12O40 content (X, wt%) were prepared, and they were applied to the dehydration of glycerin to acrolein. The effect of H3PW12O40 content on the physicochemical properties and catalytic activities of XH3PW12O40/SA nano-catalysts was investigated. Surface area and pore volume of XH3PW12O40/SA catalysts decreased with increasing H3PW12O40 content. Formation of H3PW12O40 aggregates was observed in the catalysts with high H3PW12O40 loading. Brønsted acidity of the catalysts showed a volcano-shaped trend with respect to H3PW12O40 content. It was revealed that yield for acrolein increased with increasing Brønsted acidity of XH3PW12O40/SA catalysts. Brønsted acidity of XH3PW12O40/SA catalysts served as a crucial factor determining the catalytic performance in the dehydration of glycerin. Among the catalysts tested, 25H3PW12O40/SA catalyst with the largest Brønsted acidity showed the best catalytic performance. PMID:26726511

  3. Sensitive detection of acrolein and acrylonitrile with a pulsed quantum-cascade laser

    NASA Astrophysics Data System (ADS)

    Manne, J.; Lim, A.; Tulip, J.; Jäger, W.

    2012-05-01

    We report on spectroscopic measurements of acrolein and acrylonitrile at atmospheric pressure using a pulsed distributed feedback quantum-cascade laser in combination with intra- and inter-pulse techniques and compare the results. The measurements were done in the frequency region around 957 cm-1. In the inter-pulse technique, the laser is excited with short current pulses (5-10 ns), and the pulse amplitude is modulated with an external current ramp resulting in a ˜2.3 cm-1 frequency scan. In the intra-pulse technique, a linear frequency down-chirp during the pulse is used for sweeping across the absorption line. Long current pulses up to 500 ns were used for these measurements which resulted in a spectral window of ˜2.2 cm-1 during the down-chirp. These comparatively wide spectral windows facilitated the measurements of the relatively broad absorption lines (˜1 cm-1) of acrolein and acrylonitrile. The use of a room-temperature mercury-cadmium-telluride detector resulted in a completely cryogen-free spectrometer. We demonstrate ppb level detection limits within a data acquisition time of ˜10 s with these methodologies.

  4. Elevated neutrophil elastase and acrolein-protein adducts are associated with W256 regression.

    PubMed

    Jaganjac, M; Poljak-Blazi, M; Schaur, R J; Zarkovic, K; Borovic, S; Cipak, A; Cindric, M; Uchida, K; Waeg, G; Zarkovic, N

    2012-11-01

    The involvement of granulocytes in immune response against cancer is not well understood. Depending on the cytokine milieu in which they act and on their oxidative burst, granulocytes may play either an inhibitory or stimulatory role in tumour growth. Unsaturated fatty acids, essential components of cellular membranes and storage lipids, are susceptible to granulocyte-derived reactive oxygen species (ROS). ROS can induce lipid peroxidation (LPO) resulting in the destruction of biomembranes. Thus, murine W256 tumour progressing and tumour regressing animal models were used to study the involvement of plasma inflammatory mediators and oxidative burst of circulating granulocytes in malignant destruction and detrimental tumour growth. The involvement of LPO-derived aldehydes (i.e. acrolein, 4-hydroxy-2-nonenal and malondialdehyde) and myeloperoxidase (MPO) appearance in the granulocyte anti-cancer response were further evaluated. The results obtained revealed a significant increase in neutrophil elastase in animals with regressing tumour. Furthermore, the presence of MPO in tumour microenvironment was accompanied by the formation of acrolein only 5 h after tumour transplantation and its presence increased during tumour regression. Later, at an early stage of tumour regression, the presence of other LPO-derived aldehydes were also observed. The results obtained suggest that elevated neutrophil elastase and initiation of LPO may play an important role in the tumour development leading to tumour regression.

  5. Elevated neutrophil elastase and acrolein-protein adducts are associated with W256 regression

    PubMed Central

    Jaganjac, M; Poljak-Blazi, M; Schaur, R J; Zarkovic, K; Borovic, S; Cipak, A; Cindric, M; Uchida, K; Waeg, G; Zarkovic, N

    2012-01-01

    The involvement of granulocytes in immune response against cancer is not well understood. Depending on the cytokine milieu in which they act and on their oxidative burst, granulocytes may play either an inhibitory or stimulatory role in tumour growth. Unsaturated fatty acids, essential components of cellular membranes and storage lipids, are susceptible to granulocyte-derived reactive oxygen species (ROS). ROS can induce lipid peroxidation (LPO) resulting in the destruction of biomembranes. Thus, murine W256 tumour progressing and tumour regressing animal models were used to study the involvement of plasma inflammatory mediators and oxidative burst of circulating granulocytes in malignant destruction and detrimental tumour growth. The involvement of LPO-derived aldehydes (i.e. acrolein, 4-hydroxy-2-nonenal and malondialdehyde) and myeloperoxidase (MPO) appearance in the granulocyte anti-cancer response were further evaluated. The results obtained revealed a significant increase in neutrophil elastase in animals with regressing tumour. Furthermore, the presence of MPO in tumour microenvironment was accompanied by the formation of acrolein only 5 h after tumour transplantation and its presence increased during tumour regression. Later, at an early stage of tumour regression, the presence of other LPO-derived aldehydes were also observed. The results obtained suggest that elevated neutrophil elastase and initiation of LPO may play an important role in the tumour development leading to tumour regression. PMID:23039888

  6. Dehydration of Glycerin to Acrolein Over Heteropolyacid Nano-Catalysts Supported on Silica-Alumina.

    PubMed

    Kang, Tae Hun; Choi, Jung Ho; Choi, Jun Seon; Song, In Kyu

    2015-10-01

    A series of H3PW12O40 nano-catalysts supported on silica-alumina (XH3PW12O40/SA (X = 10, 15, 20, 25, and 30)) with different H3PW12O40 content (X, wt%) were prepared, and they were applied to the dehydration of glycerin to acrolein. The effect of H3PW12O40 content on the physicochemical properties and catalytic activities of XH3PW12O40/SA nano-catalysts was investigated. Surface area and pore volume of XH3PW12O40/SA catalysts decreased with increasing H3PW12O40 content. Formation of H3PW12O40 aggregates was observed in the catalysts with high H3PW12O40 loading. Brønsted acidity of the catalysts showed a volcano-shaped trend with respect to H3PW12O40 content. It was revealed that yield for acrolein increased with increasing Brønsted acidity of XH3PW12O40/SA catalysts. Brønsted acidity of XH3PW12O40/SA catalysts served as a crucial factor determining the catalytic performance in the dehydration of glycerin. Among the catalysts tested, 25H3PW12O40/SA catalyst with the largest Brønsted acidity showed the best catalytic performance.

  7. 29 CFR 1915.1048 - Formaldehyde.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 29 Labor 7 2010-07-01 2010-07-01 false Formaldehyde. 1915.1048 Section 1915.1048 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR (CONTINUED) OCCUPATIONAL SAFETY AND HEALTH STANDARDS FOR SHIPYARD EMPLOYMENT Toxic and Hazardous Substances §...

  8. Formaldehyde and hydroperoxides at Mauna Loa Observatory

    NASA Astrophysics Data System (ADS)

    Heikes, Brian G.

    1992-11-01

    Measurements of formaldehyde, hydrogen peroxide, and a measure of organic hydroperoxides are presented. Modifications are described for the dual-enzyme H2O2 technique. These modifications facilitate the quantification of soluble ROOH and H2O2, the analysis of O3-H2O2 artifact, and catalase H2O2 residual.

  9. A passive sampler for airborne formaldehyde

    NASA Astrophysics Data System (ADS)

    Grosjean, Daniel; Williams, Edwin L.

    A simple, inexpensive passive sampler is described that is capable of reliable measurements of formaldehyde at the parts per billion (ppb) levels relevant to indoor and outdoor air quality. The passive sampler consists of a modified dual filter holder in which the upper stage serves as the diffusion barrier, the lower stage includes a 2,4-dinitrophenylhydrazine (DNPH)-coated filter which collects formaldehyde, and the space between the two stages serve as the diffusion gap. The measured sampling rate, 18.8 ± 1.8 ml min -1, was determined in experiments involving sampling of ppb levels of formaldehyde with the passive sampler and with DNPH-coated C 18 cartridges and agrees well with the value of 19.4 ± 2.0 ml min -1 calculated from theory. The measured sampling rate was independent of formaldehyde concentration (16-156 ppb) and sampling duration (1.5-72 h). The precision of the measurements for colocated passive samplers averaged 8.6% in purified and indoor air (office and museums) and 10.2% in photochemically polluted outdoor air. With a 1.2-μm pore size Teflon filter as the diffusion barrier, the detection limit is 32 ppb h, e.g. 4 ppb in an 8-h sample, 1.3 ppb in a 24-h sample, and so on. Perceived advantages and limitations of the sampler are discussed including flexibility, cost effectiveness and possible negative bias at high ambient levels of ozone.

  10. Edible carbohydrates from formaldehyde in a spacecraft

    NASA Technical Reports Server (NTRS)

    Weiss, A. H.

    1975-01-01

    The autocatalytic nature of the base catalyzed condensation of formaldehyde to formose sugars is eliminated by using as a cocatalyst, an aldose, or ketose having an alpha-hydrogen. This is more strongly complexed by base than is formaldehyde and the cocatalyst and sugar products accumulate as catalyst complexes instead of formaldehyde. Because of the presence of alpha-hydrogen atoms in cocatalysts and formose sugars, their removal by cross Cannizzaro reaction of complexed sugars does not occur, so the formose reaction behaves autocatalytically due to this accumulation. It is believed that a given catalytic formose complex is not a discrete complexed sugar, but rather, a scrambled dynamic mixture of sugars having weakened structures. The sugar complexes derive from a common salt-like formaldehyde complex, which, because of the absence of alpha-hydrogen, has a greater tendency to undergo Cannizzaro reaction, rather than formose condensation. Because of this, the Cannizzaro reaction can proceed without measurable formose condensation. The reverse is not possible.

  11. Gypsum Wallboard as a sink for formaldehyde

    EPA Science Inventory

    Formaldehyde (HCHO) has been of special concern as an indoor air pollutant because of its presence in a wide range of consumer products and its adverse health effects. Materials acting as HCHO sinks, such as painted gypsum wallboard, can become emission sources. However, adsorpti...

  12. 29 CFR 1910.1048 - Formaldehyde.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... MSDSs if these items may constitute a health hazard within the meaning of 29 CFR 1910.1200(d) under... result in new or additional exposure to formaldehyde. (iii) If the employer receives reports of signs or... conditions. (4) Termination of monitoring. The employer may discontinue periodic monitoring for employees...

  13. Electrospinning formaldehyde cross-linked zein solutions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In order to develop zein fibers with improved physical properties and solvent resistance, formaldehyde was used as the cross-linking reagent before spinning. The cross-linking reaction was carried out in either acetic acid or ethanolic-HCl where the amount of cross-linking reagent was between 1 and...

  14. 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...

  15. 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...

  16. Decrease of reduced glutathione in isolated rat hepatocytes caused by acrolein, acrylonitrile, and the thermal degradation products of styrene copolymers.

    PubMed

    Zitting, A; Heinonen, T

    1980-01-01

    Decrease of reduced glutathione (GSH) was induced in isolated rat hepatocytes by incubation with acrolein or acrylonitrile for 120 min or exposure to the products of oxidative thermal degradation of acrylonitrile-butadiene-styrene copolymer (ABS), styrene-acrylonitrile copolymer (SAN), and high impact polystyrene (SB). The decrease of GSH by acrolein was rapid but the cells soon recovered at acrolein concentrations of 0.025--0.25 mM. 0.5 mM acrolein depleted the cells of GSH and they were uncapable of further GSH synthesis. At concentrations of 0.25--0.5 mM concomitant lipid peroxidation impaired the integrity of the cell membranes. Also acrylonitrile induced a dose dependent GSH decrease at concentrations of 0.05--1 mM. Neither membrane damage nor lipid peroxidation was detected during 120-min incubations at these acrylonitrile concentrations. The thermal degradation products of ABS, SAN and SB caused a decrease of GSH in hepatocytes. The extent of the decrease depended on the degradation temperature and the type of the plastic. The membrane integrity was impaired in the cases where GSH was depleted almost completely; ABS degraded at 350 degrees C and SB at 250 degrees C. The measurements of lipid peroxidation by the thiobarbituric acid and the diene conjugation methods were impossible because the degradation products contained compounds which interfered with these tests.

  17. The adsorption of acrolein on a Pt (1 1 1): A study of chemical bonding and electronic structure

    NASA Astrophysics Data System (ADS)

    Pirillo, S.; López-Corral, I.; Germán, E.; Juan, A.

    2012-12-01

    The adsorption of acrolein on a Pt (1 1 1) surface was studied using ab-initio and semiempirical calculations. Geometry optimization and densities of states (DOS) curves were carried out using the Vienna Ab-initio Simulation Package (VASP) code. We started our study with the preferential geometries corresponding to the different acrolein/Pt (1 1 1) adsorption modes previously reported. Then, we examined the evolution of the chemical bonding in these geometries, using the crystal orbital overlap population (COOP) and overlap population (OP) analysis of selected pairs of atoms. We analyzed the acrolein intramolecular bonds, Pt (1 1 1) superficial bonds and new moleculesbnd surface formed bonds after adsorption. We found that Ptsbnd Pt bonds interacting with the molecule and acrolein Cdbnd O and Cdbnd C bonds are weakened after adsorption; this last bond is significantly linked to the surface. The obtained Csbnd Pt and Osbnd Pt OP values suggest that the most stable adsorption modes are η3-cis and η4-trans, while the η1-trans is the less favored configuration. We also found that C pz orbital and Pt pz and d orbitals participate strongly in the adsorption process.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  19. 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.

  20. 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

    2014-04-01

    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).

  1. Development of melamine-formaldehyde resin microcapsules with low formaldehyde emission suited for seed treatment.

    PubMed

    Yuan, Huizhu; Li, Guangxing; Yang, Lijuan; Yan, Xiaojing; Yang, Daibin

    2015-04-01

    To reduce the application frequency and improve the efficacy of insecticides, melamine-formaldehyde (MF) resin microcapsules suited for seed treatment containing a mixture of fipronil and chlorpyrifos were prepared by in situ polymerization. A formaldehyde/melamine molar ratio of 4:1 yielded microcapsules with the smallest size and the most narrow size distribution. The level of unreacted formaldehyde in the microcapsule suspension increased proportionally with the F/M molar ratio. When the MF resin microcapsule suspension was used as a seed treatment to coat peanut seeds, the unreacted formaldehyde did not significantly inhibit the seedling emergence, but the ongoing release of formaldehyde generated from the degradation of MF resins played an important role in inhibiting emergence. Melamine was shown to be an effective formaldehyde scavenger that mitigated this inhibition when it was incorporated within the microcapsule wall. Field experiments showed that MF-resin-encapsulated mixtures of fipronil and chlorpyrifos have much greater efficacies against white grubs than the conventional formulation.

  2. 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

  3. Subchronic (12-week) inhalation toxicity study of methanol-fueled engine exhaust in rats

    SciTech Connect

    Maejima, Kazuhito; Suzuki, Tadao ); Numata, Hiroaki ); Maekawa, Akihiko ); Nagase, Sumi ); Ishinishi, Noburu )

    1994-01-01

    To evaluate the inhalation toxicity to rats of exhaust at low concentration for longer periods, Fischer 344 rats were exposed to 3 concentrations of exhaust generated by an M85 methanol-fueled engine (methanol with 15% gasoline) without catalyst for 8 h/d, 6 d/wk for 4, 8, or 12 wk. Concentration- and time-dependent increase carboxyhemoglobin in the erythrocytes and decrease in cytochrome P-450 in the lungs were observed in all treated groups. Furthermore, significant increases in plasma formaldehyde were observed in the group exposed to the highest concentration of exhaust (carbon monoxide, 89.8 ppm; formaldehyde, 2.3 ppm; methanol, 8.1 ppm; nitrogen oxides, 22.9 ppm; nitrogen dioxide, 1.1 ppm) for 8 or 12 wk. No change of plasma folic acid was observed in any group, and no methanol or formic acid was detected in the plasma in any animals. Histopathologically, exposure-related changes were found only in the nasal cavity of the high-concentration group. Slight hyperplasia/squamous metaplasias of the respiratory epithelium lining the nasoturbinate and maxilloturbinate were observed after 4 wk of exposure, and the incidences and degrees of these lesions increased slightly with the exposure time. No changes were found in the olfactory epithelium of the nasal cavity. As judged by optical microscopy, the exhaust concentration with no effect on the nasal cavity under the experimental conditions was concluded to be the medium concentration level containing 0.55 ppm formaldehyde. In the present study, however, concentration- and time-dependent increase of carboxyhemoglobin in the erythrocytes and decrease of the lung P-450 level were observed. Therefore, further study on more long-term inhalation of lower concentrations of exhaust might be needed. 31 refs., 2 figs., 3 tabs.

  4. Toxic effects of formaldehyde on the urinary system.

    PubMed

    İnci, Mehmet; Zararsız, İsmail; Davarcı, Mürsel; Görür, Sadık

    2013-03-01

    Formaldehyde is a chemical substance with a pungent odor that is highly soluble in water and occurs naturally in organisms. Formaldehyde, when taken into organisms, is metabolized into formic acid in the liver and erythrocytes and is then excreted, either with the urine and feces or via the respiratory system. Form-aldehyde is widely used in the industrial and medical fields, and employees in these sectors are frequently exposed to it. Anatomists and medical students are affected by formaldehyde gas during dissection lessons. Because full protection from formaldehyde is impossible for employees in industrial plants using this chemical and for workers in laboratory conditions, several measures can be implemented to prevent and/or reduce the toxic effects of formaldehyde. In this review, we aimed to identify the toxic effects of formaldehyde on the urinary system.

  5. Toxic effects of formaldehyde on the urinary system

    PubMed Central

    İnci, Mehmet; Zararsız, İsmail; Davarcı, Mürsel; Görür, Sadık

    2013-01-01

    Formaldehyde is a chemical substance with a pungent odor that is highly soluble in water and occurs naturally in organisms. Formaldehyde, when taken into organisms, is metabolized into formic acid in the liver and erythrocytes and is then excreted, either with the urine and feces or via the respiratory system. Form-aldehyde is widely used in the industrial and medical fields, and employees in these sectors are frequently exposed to it. Anatomists and medical students are affected by formaldehyde gas during dissection lessons. Because full protection from formaldehyde is impossible for employees in industrial plants using this chemical and for workers in laboratory conditions, several measures can be implemented to prevent and/or reduce the toxic effects of formaldehyde. In this review, we aimed to identify the toxic effects of formaldehyde on the urinary system. PMID:26328078

  6. MMENT>Computational study of complete methanol dehydrogenation on Au(100) and Au(310) surfaces: Dominant role of atomic oxygen

    NASA Astrophysics Data System (ADS)

    Hussain, A.; Shah, S. H.

    2014-02-01

    Methanol dehydrogenation to CO and H2 has been systematically investigated on Au(100) and Au(310) surfaces using density functional theory (DFT). All possible intermediates involved are calculated. Methanol and formaldehyde being saturated molecules adsorb weakly on both the surfaces. The thermochemistry and kinetics of the decomposition via sequential hydrogen abstraction are both found to be highly unfavorable for these species. Nevertheless, atomic oxygen pre-covered surfaces substantially enhance CH3OH and CH2O (resulting in CH2O2 complex formation) interaction with Au and offer weak activation barrier for methanol disintegration into CH3O and H. On the other hand, methoxy, formyl, and atomic hydrogen are predicted to make strong chemical bonds with the clean Au surfaces. The abstraction of hydrogen from the methoxy intermediate on bare gold surfaces is practical, while formyl splits instantaneously during optimization. A feasible mechanism on oxygen pre-covered surfaces for complete methanol dehydrogenation has been presented.

  7. Elution behavior of oligomers on a polyvinyl alcohol gel column with chloroform, methanol, and their mixtures

    SciTech Connect

    Mori, S. )

    1988-01-01

    Elution phenomena of size exclusion chromatography (SEC) plus superimposed adsorption effects for oligostyrenes, epoxy resins, methylated melamine-formaldehyde resin prepolymers, p-cresol-formaldehyde resin prepolymers, and phenol-formaldehyde resin prepolymers were investigated. SEC and superimposed adsorption effects could be elucidated from a concept of solubility parameter. Minimum retention volumes of these obligomers were obtained with the mobile phases of chloroform/methanol, 80/20 or 60/40 (v/v), and separation was expected to be mostly performed by SEC. The solubility parameter of polyvinyl alcohol gels was estimated to be between 21 and 23 from the above results. Elution for normal phase chromatography was in the order of increasing molecular weight and that for reversed-phase chromatography was in the order of decreasing molecular weight. These are reversed phenomena to those for low-molecular weigh compounds. Solubility of sample solutes to mobile phase must be considered. Methanol mobile phase-polyvinyl alcohol gel system might be exception.

  8. Threshold for occluded formaldehyde patch test in formaldehyde-sensitive patients. Relationship to repeated open application test with a product containing formaldehyde releaser.

    PubMed

    Flyvholm, M A; Hall, B M; Agner, T; Tiedemann, E; Greenhill, P; Vanderveken, W; Freeberg, F E; Menné, T

    1997-01-01

    Our purpose was to investigate the eliciting threshold concentration of formaldehyde in formaldehyde-sensitive individuals in the occluded and non-occluded patch test, and to evaluate the relationship to repeated open application test (ROAT) with a product containing a formaldehyde releaser. 20 formaldehyde-sensitive patients and a control group of 20 healthy volunteers were included in the study. Occluded and non-occluded patch tests with formaldehyde solutions from 25 to 10,000 ppm, and ROAT for 1 week with a leave-on cosmetic product containing on average 300 ppm formaldehyde, were carried out simultaneously on each subject. In the occluded patch test, 1/2 of the 20 patients only reacted to 10,000 ppm formaldehyde, 9 reacted to 5,000 ppm, 3 reacted to 1,000 ppm, 2 reacted to 500 ppm and 1 reacted to 250 ppm. No definite positive reactions were observed in the non-occluded patch test or in the ROAT. No positive reactions were observed in the control group to any of the test procedures. We concluded that the threshold concentration for occluded patch test to formaldehyde in formaldehyde-sensitive patients was 250 ppm. The threshold in occluded patch test corresponded to the degree of sensitivity. Definite positive reactions in the ROAT were not seen, either indicating that they are unlikely to happen with the type of product used or that the exposure time was too short.

  9. The enzymatic reaction-induced configuration change of the prosthetic group PQQ of methanol dehydrogenase.

    PubMed

    Li, Jie; Gan, Jian-Hua; Mathews, F Scott; Xia, Zong-Xiang

    2011-03-25

    Methanol dehydrogenase is a heterotetrameric enzyme containing the prosthetic group pyrroloquinoline quinone (PQQ), which catalyzes the oxidation of methanol to formaldehyde. The crystal structure of methanol dehydrogenase from Methylophilus W3A1, previously determined at high resolution, exhibits a non-planar configuration of the PQQ ring system and lends support for a hydride transfer mechanism of the enzymatic reaction catalyzed by the enzyme. To investigate why PQQ is in the C5-reduced form and to better understand the catalytic mechanism of the enzyme, three structures of this enzyme in a new crystal form have been determined at higher resolution. Two of the three crystals were grown in the presence of 1 and 50 mM methanol, respectively, both structures of which show non-planar configurations of the PQQ ring system, confirming the previous conclusion; the other was crystallized in the presence of 50 mM ethanol, the structure of which displays a planar ring system for PQQ. Comparison of these structures reveals that the configuration change of PQQ is induced by the enzymatic reaction. The reaction takes place and the C5-reduced PQQ intermediate is produced when the enzyme co-crystallizes with methanol, but the enzymatic reaction does not take place and the PQQ ring retains a planar configuration of the oxidized orthoquinone form when ethanol instead of methanol is present in the crystallization solution.

  10. Methanol simplifies gas processing

    SciTech Connect

    Minkkinen, A.; Jonchere, J.P.

    1997-12-31

    Recent development of a simple single solvent technology goes far to meet the complete gas processing needs. The use of methanol, as practiced in the IPFEXOL process, where it is used not only as a hydrate inhibitor and antifreeze agent but as an acid gas extraction solvent makes the complete gas processing scheme simple and probably the most cost effective as well. This paper presents several gas processing applications where water, hydrocarbon liquids and acid gases are removed from natural wellhead production gases. Water and hydrocarbon liquids removal is achieved to the extent necessary to make a pipeline transportable gas or meet downstream cryogenic processing demands. These are illustrated with recent applications of the IFPEX-1 process successfully operating today in North America and the Far East. A recent North Sea offshore project is highlighted showing the particular advantages in offshore applications. For the removal of water and hydrocarbon liquids together with a substantial quantity of not only CO{sub 2} but H{sub 2}S, the most complete methanol use scheme is presented. This is illustrated with the development of an advanced version of the IFPEX-2 process containing some innovative but simple equipment concepts which yields high pressure dry acid gases for reinjection or a high quality acid gas destined to Claus type sulfur recovery.

  11. Sources and seasonality of atmospheric methanol based on tall tower measurements in the US Upper Midwest

    NASA Astrophysics Data System (ADS)

    Hu, L.; Millet, D. B.; Mohr, M. J.; Wells, K. C.; Griffis, T. J.; Helmig, D.

    2011-11-01

    We present over one year (January 2010-February 2011) of continuous atmospheric methanol measurements from the University of Minnesota tall tower Trace Gas Observatory (KCMP tall tower; 244 m a.g.l.), and interpret the dataset in terms of constraints on regional methanol sources and seasonality. The seasonal cycle of methanol concentrations observed at the KCMP tall tower is generally similar to that simulated by a global 3-D chemical transport model (GEOS-Chem, driven with MEGANv2.0 biogenic emissions) except the seasonal peak occurs ~1 month earlier in the observations, apparently reflecting a model underestimate of emission rates for younger versus older leaves. Based on a source tracer approach, which we evaluate using GEOS-Chem and with multiple tracers, we estimate that anthropogenic emissions account for approximately 40% of ambient methanol abundance during winter and 10% during summer. During daytime in summer, methanol concentrations increase exponentially with temperature, reflecting the temperature sensitivity of the biogenic source, and the observed temperature dependence is statistically consistent with that in the model. Nevertheless, summertime concentrations are underestimated by on average 35% in the model for this region. The seasonal importance of methanol as a source of formaldehyde (HCHO) and carbon monoxide (CO) is highest in spring through early summer, when biogenic methanol emissions are high but isoprene emissions are still relatively low. During that time observed methanol concentrations account for on average 20% of the total CO and HCHO production rates as simulated by GEOS-Chem, compared to 12% later in the summer and 12% on an annual average basis. The biased seasonality in the model means that the photochemical role for methanol early in the growing season is presently underestimated.

  12. Sources and seasonality of atmospheric methanol based on tall tower measurements in the US Upper Midwest

    NASA Astrophysics Data System (ADS)

    Hu, L.; Mohr, M. J.; Wells, K. C.; Griffis, T. J.; Helmig, D.; Millet, D. B.

    2011-06-01

    We present over one year of continuous atmospheric methanol measurements from the University of Minnesota tall tower Trace Gas Observatory (KCMP tall tower; 244 m a.g.l.), and interpret the dataset in terms of constraints on regional methanol sources and seasonality. The seasonal cycle of methanol concentrations observed at the KCMP tall tower is generally similar to that simulated by a global 3-D chemical transport model (GEOS-Chem, driven with MEGANv2.0 biogenic emissions) except the seasonal peak occurs ~1 month earlier in the observations, apparently reflecting a model underestimate of emission rates for younger versus older leaves. Based on a source tracer approach, which we evaluate using GEOS-Chem and with multiple tracers, we estimate that anthropogenic emissions account for approximately 40 % of ambient methanol abundance during winter and 10 % during summer. During daytime in summer, methanol concentrations increase exponentially with temperature, reflecting the temperature sensitivity of the biogenic source, and the observed temperature dependence is statistically consistent with that in the model. Nevertheless, summertime concentrations are underestimated by on average 35 % in the model for this region. The seasonal importance of methanol as a source of formaldehyde (HCHO) and carbon monoxide (CO) is highest in spring through early summer, when biogenic methanol emissions are high but isoprene emissions are still relatively low. During that time observed methanol concentrations account for on average 20 % of the total CO and HCHO production rates as simulated by GEOS-Chem, compared to 12 % later in the summer and 12 % on an annual average basis. The biased seasonality in the model means that the photochemical role for methanol early in the growing season is presently underestimated.

  13. Cytotoxicity of Thirdhand Smoke and Identification of Acrolein as a Volatile Thirdhand Smoke Chemical That Inhibits Cell Proliferation.

    PubMed

    Bahl, Vasundhra; Weng, Nikki J-H; Schick, Suzaynn F; Sleiman, Mohamad; Whitehead, Jacklyn; Ibarra, Allison; Talbot, Prue

    2016-03-01

    Thirdhand smoke (THS) is a mixture of chemicals that remain on indoor surfaces after smoking has ceased. These chemicals can be inhaled, ingested, or absorbed dermally, and thus could impact human health. We evaluated the cytotoxicity and mode of action of fresh and aged THS, the toxicity of volatile organic chemicals (VOCs) in THS, and the molecular targets of acrolein, a VOC in THS. Experiments were done using mouse neural stem cells (mNSC), human pulmonary fibroblasts (hPF), and lung A549 epithelial cells. THS-exposed cotton cloth was extracted in Dulbecco's Eagle Medium and caused cytotoxicity in the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. THS extracts induced blebbing, immotility, vacuolization, cell fragmentation, severing of microfilaments and depolymerization of microtubules in mNSC. Cytotoxicity was inversely related to headspace volume in the extraction container and was lost upon aging, suggesting that VOCs in THS were cytotoxic. Phenol, 2',5'-dimethyl furan and acrolein were identified as the most cytotoxic VOCs in THS, and in combination, their cytotoxicity increased. Acrolein inhibited proliferation of mNSC and hPF and altered expression of cell cycle regulatory genes. Twenty-four hours of treatment with acrolein decreased expression of transcription factor Dp-1, a factor needed for the G1 to S transition in the cell cycle. At 48 h, WEE1 expression increased, while ANACP1 expression decreased consistent with blocking entry into and completion of the M phase of the cell cycle. This study identified acrolein as a highly cytotoxic VOC in THS which killed cells at high doses and inhibited cell proliferation at low doses. PMID:26719373

  14. Polyphenol extract from Phellinus igniarius protects against acrolein toxicity in vitro and provides protection in a mouse stroke model.

    PubMed

    Suabjakyong, Papawee; Saiki, Ryotaro; Van Griensven, Leo J L D; Higashi, Kyohei; Nishimura, Kazuhiro; Igarashi, Kazuei; Toida, Toshihiko

    2015-01-01

    The basidiomycetous mushroom Phellinus igniarius (L.) Quel. has been used as traditional medicine in various Asian countries for many years. Although many reports exist on its anti-oxidative and anti-inflammatory activities and therapeutic effects against various diseases, our current knowledge of its effect on stroke is very limited. Stroke is a neurodegenerative disorder in which oxidative stress is a key hallmark. Following the 2005 discovery by Igarashi's group that acrolein produced from polyamines in vivo is a major cause of cell damage by oxidative stress, we now describe the effects of anti-oxidative extracts from P. igniarius on symptoms of experimentally induced stroke in mice. The toxicity of acrolein was compared with that of hydrogen peroxide in a mouse mammary carcinoma cell line (FM3A). We found that the complete inhibition of FM3A cell growth by 5 μM acrolein could be prevented by crude ethanol extract of P. igniarius at 0.5 μg/ml. Seven polyphenol compounds named 3,4-dihydroxybenzaldehyde, 4-(3,4-dihydroxyphenyl-3-buten-2one, inonoblin C, phelligridin D, inoscavin C, phelligridin C and interfungin B were identified from this ethanolic extract by LCMS and 1H NMR. Polyphenol-containing extracts of P. igniarius were then used to prevent acrolein toxicity in a mouse neuroblastoma (Neuro-2a) cell line. The results suggested that Neuro-2a cells were protected from acrolein toxicity at 2 and 5 μM by this polyphenol extract at 0.5 and 2 μg/ml, respectively. Furthermore, in mice with experimentally induced stroke, intraperitoneal treatment with P. igniarius polyphenol extract at 20 μg/kg caused a reduction of the infarction volume by 62.2% compared to untreated mice. These observations suggest that the polyphenol extract of P. igniarius could serve to prevent ischemic stroke. PMID:25811373

  15. Polyphenol extract from Phellinus igniarius protects against acrolein toxicity in vitro and provides protection in a mouse stroke model.

    PubMed

    Suabjakyong, Papawee; Saiki, Ryotaro; Van Griensven, Leo J L D; Higashi, Kyohei; Nishimura, Kazuhiro; Igarashi, Kazuei; Toida, Toshihiko

    2015-01-01

    The basidiomycetous mushroom Phellinus igniarius (L.) Quel. has been used as traditional medicine in various Asian countries for many years. Although many reports exist on its anti-oxidative and anti-inflammatory activities and therapeutic effects against various diseases, our current knowledge of its effect on stroke is very limited. Stroke is a neurodegenerative disorder in which oxidative stress is a key hallmark. Following the 2005 discovery by Igarashi's group that acrolein produced from polyamines in vivo is a major cause of cell damage by oxidative stress, we now describe the effects of anti-oxidative extracts from P. igniarius on symptoms of experimentally induced stroke in mice. The toxicity of acrolein was compared with that of hydrogen peroxide in a mouse mammary carcinoma cell line (FM3A). We found that the complete inhibition of FM3A cell growth by 5 μM acrolein could be prevented by crude ethanol extract of P. igniarius at 0.5 μg/ml. Seven polyphenol compounds named 3,4-dihydroxybenzaldehyde, 4-(3,4-dihydroxyphenyl-3-buten-2one, inonoblin C, phelligridin D, inoscavin C, phelligridin C and interfungin B were identified from this ethanolic extract by LCMS and 1H NMR. Polyphenol-containing extracts of P. igniarius were then used to prevent acrolein toxicity in a mouse neuroblastoma (Neuro-2a) cell line. The results suggested that Neuro-2a cells were protected from acrolein toxicity at 2 and 5 μM by this polyphenol extract at 0.5 and 2 μg/ml, respectively. Furthermore, in mice with experimentally induced stroke, intraperitoneal treatment with P. igniarius polyphenol extract at 20 μg/kg caused a reduction of the infarction volume by 62.2% compared to untreated mice. These observations suggest that the polyphenol extract of P. igniarius could serve to prevent ischemic stroke.

  16. α,β-Unsaturated aldehyde pollutant acrolein suppresses cardiomyocyte contractile function: Role of TRPV1 and oxidative stress.

    PubMed

    Wu, Zhenbiao; He, Emily Y; Scott, Glenda I; Ren, Jun

    2015-01-01

    Air pollution is associated with an increased prevalence of heart disease and is known to trigger a proinflammatory response via stimulation of transient receptor potential vanilloid cation channels (TRPV1, also known as the capsaicin receptor). This study was designed to examine the effect of acrolein, an essential α,β-unsaturated aldehyde pollutant, on myocardial contractile function and the underlying mechanism involved with a focus on TRPV1 and oxidative stress. Cardiomyocyte mechanical and intracellular Ca(2+) properties were evaluated using an IonOptix MyoCam® system including peak shortening (PS), maximal velocity of shortening/relengthening (± dL/dt), time-to-PS (TPS), time-to-90% relengthening (TR90 ), fura-2 fluorescence intensity (FFI) and intracellular Ca(2+) decay. Changes in apoptosis and TRPV1 were evaluated using Western blot analysis. The degree of oxidative stress was assessed using the ratio between reduced and oxidized glutathione. Results obtained revealed that exposure of cardiomyocytes to acrolein acutely compromised contractile and intracellular Ca(2+) properties including depressed PS, ± dL/dt and ΔFFI, as well as prolonged TR90 and intracellular Ca(2+) decay. In addition, acrolein exposure upregulated TRPV1 associated with an increase in both apoptosis and oxidative stress. However, the acrolein-induced cardiomyocyte contractile and intracellular Ca(2+) anomalies, as well as apoptosis (as evidenced by Bcl-2, Bax, FasL, Caspase-3 and -8), were negated by the reactive oxygen species (ROS) scavenger glutathione or the TRPV1 antagonist capsazepine. Collectively these data suggest that the α,β-unsaturated aldehyde pollutant acrolein may play a role in the pathogenesis and sequelae of air pollution-induced heart disease via a TRPV1- and oxidative stress-dependent mechanism.

  17. A single exposure to acrolein desensitizes baroreflex responsiveness and increases cardiac arrhythmias in normotensive and hypertensive rats.

    PubMed

    Hazari, Mehdi S; Griggs, Jennifer; Winsett, Darrell W; Haykal-Coates, Najwa; Ledbetter, Allen; Costa, Daniel L; Farraj, Aimen K

    2014-03-01

    Short-term exposure to air pollutants has been linked to acute cardiovascular morbidity and mortality. Even in the absence of overt signs or symptoms, pollutants can cause subtle disruptions to internal compensatory mechanisms, which maintain homeostatic balance in response to various environmental and physiological stressors. We hypothesized that a single exposure to acrolein, a ubiquitous gaseous air pollutant, would decrease the sensitivity of baroreflex (BRS), which maintains blood pressure by altering heart rate (HR), modify cardiac electrophysiological properties and increase arrhythmia in rats. Wistar-Kyoto normotensive (WKY) and spontaneously hypertensive (SH) rats implanted with radiotelemeters and a chronic jugular vein catheter were tested for BRS using phenylephrine and sodium nitroprusside 2 days before and 1 h after whole-body exposure to 3 ppm acrolein (3 h). HR and electrocardiogram (ECG) were continuously monitored for the detection of arrhythmia in the pre-exposure, exposure and post-exposure periods. Whole-body plethysmography was used to continuously monitor ventilation in conscious animals. SH rats had higher blood pressure, lower BRS and increased frequency of AV block as evidence by non-conducted p-waves when compared with WKY rats. A single exposure to acrolein caused a decrease in BRS and increased incidence of arrhythmia in both WKY and SH rats. There were minimal ECG differences between the strains, whereas only SH rats experienced irregular breathing during acrolein. These results demonstrate that acrolein causes immediate cardiovascular reflexive dysfunction and persistent arrhythmia in both normal and hypertensive animals. As such, homeostatic imbalance may be one mechanism by which air pollution increases risk 24 h after exposure, particularly in people with underlying cardiovascular disease.

  18. Polyphenol Extract from Phellinus igniarius Protects against Acrolein Toxicity In Vitro and Provides Protection in a Mouse Stroke Model

    PubMed Central

    Suabjakyong, Papawee; Saiki, Ryotaro; Van Griensven, Leo J. L. D.; Higashi, Kyohei; Nishimura, Kazuhiro; Igarashi, Kazuei; Toida, Toshihiko

    2015-01-01

    The basidiomycetous mushroom Phellinus igniarius (L.) Quel. has been used as traditional medicine in various Asian countries for many years. Although many reports exist on its anti-oxidative and anti-inflammatory activities and therapeutic effects against various diseases, our current knowledge of its effect on stroke is very limited. Stroke is a neurodegenerative disorder in which oxidative stress is a key hallmark. Following the 2005 discovery by Igarashi’s group that acrolein produced from polyamines in vivo is a major cause of cell damage by oxidative stress, we now describe the effects of anti-oxidative extracts from P. igniarius on symptoms of experimentally induced stroke in mice. The toxicity of acrolein was compared with that of hydrogen peroxide in a mouse mammary carcinoma cell line (FM3A). We found that the complete inhibition of FM3A cell growth by 5 μM acrolein could be prevented by crude ethanol extract of P. igniarius at 0.5 μg/ml. Seven polyphenol compounds named 3,4-dihydroxybenzaldehyde, 4-(3,4-dihydroxyphenyl-3-buten-2one, inonoblin C, phelligridin D, inoscavin C, phelligridin C and interfungin B were identified from this ethanolic extract by LCMS and 1H NMR. Polyphenol-containing extracts of P. igniarius were then used to prevent acrolein toxicity in a mouse neuroblastoma (Neuro-2a) cell line. The results suggested that Neuro-2a cells were protected from acrolein toxicity at 2 and 5 μM by this polyphenol extract at 0.5 and 2 μg/ml, respectively. Furthermore, in mice with experimentally induced stroke, intraperitoneal treatment with P. igniarius polyphenol extract at 20 μg/kg caused a reduction of the infarction volume by 62.2% compared to untreated mice. These observations suggest that the polyphenol extract of P. igniarius could serve to prevent ischemic stroke. PMID:25811373

  19. Effectiveness of various methods of formaldehyde neutralization using monoethanolamine.

    PubMed

    Coskey, Andrew; Gest, Thomas R

    2015-05-01

    Formaldehyde is the most commonly used fixative chemical for the preservation of human cadavers used for educational purposes in the United States. Formaldehyde is also a known carcinogenic agent whose exposure level is regulated by guidelines of the Occupational Safety and Health Administration. Various methods for formaldehyde neutralization exist, yet many donations programs do not take any steps to neutralize the formaldehyde in embalmed donor bodies. The effectiveness of monoethanolamine (MEA) in neutralizing formaldehyde is well documented when used as a final injection during embalming. The purpose of this study is to report the effectiveness of several post-embalming techniques of formaldehyde neutralization. Twenty-four donor bodies were assigned to four experimental groups of six. For the three experimental groups, the techniques tested involve delivery of a 20:1 dilution of deionized water:MEA via recannulization and gravity flow infusion, compartment injection, and alternate wetting solution containing four percent MEA. Our results indicated that spray bottle delivery was not effective in neutralization of formaldehyde compared to the control group, but that formaldehyde levels decreased when recannulization or compartment injection were used. The most effective method of formaldehyde neutralization was compartment injection of MEA solution (P < 0.01). The results of this study indicate that, in situations where MEA is not used as a final infusion during embalming, compartment injection of MEA solution is an effective method of formaldehyde neutralization.

  20. 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...

  1. 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.

  2. Exploitation of pulsed flows for on-line dispersive liquid-liquid microextraction: Spectrophotometric determination of formaldehyde in milk.

    PubMed

    Nascimento, Carina F; Brasil, Marcos A S; Costa, Susana P F; Pinto, Paula C A G; Saraiva, Maria Lúcia M F S; Rocha, Fábio R P

    2015-11-01

    Formaldehyde is often added to foods as a preservative, but it is highly toxic to humans, having been identified as a carcinogenic substance. It has also been used for the adulteration of milk in order to diminish the bacteria count and increase the shelf life of the product. Herein, we present a green dispersive liquid-liquid microextraction procedure in a flow-batch system for the determination of formaldehyde in milk. Pulsed flows were exploited for the first time to improve the dispersion of the extractant in the aqueous phase. The Hantzsch reaction was used for the derivatization of formaldehyde and the product was extracted with the ionic liquid (IL) trihexyltetradecylphosphonium chloride with methanol as the disperser. The flow-batch chamber was made of stainless steel with the facility for resistive heating to speed up the derivatization reaction. Spectrophotometric measurements were directly carried out in the organic phase using an optical fiber spectrophotometer. The limit of detection and coefficient of variation were 100 μg L(-1) and 3.1% (n=10), respectively, with a linear response from 0.5 to 5.0 mg L(-1), described by the equation A=0.088+0.116CF (mg L(-1)) in which A is absorbance and CF is formaldehyde concentration in mg L(-1). The estimated recoveries of formaldehyde from spiked milk samples ranged from 91% to 106% and the slopes of the analytical curves obtained with reference solutions in water or milk were in agreement, thus indicating the absence of matrix effects. Accuracy was demonstrated by the agreement of the results with those achieved by the reference fluorimetric procedure at the 95% confidence level. The proposed procedure allows for 10 extractions per hour, with minimized reagent consumption (120 μL of IL and 3.5 μL acetylacetone) and generation of only 6.7 mL waste per determination, which contribute to the eco-friendliness of the procedure. PMID:26452946

  3. Exploitation of pulsed flows for on-line dispersive liquid-liquid microextraction: Spectrophotometric determination of formaldehyde in milk.

    PubMed

    Nascimento, Carina F; Brasil, Marcos A S; Costa, Susana P F; Pinto, Paula C A G; Saraiva, Maria Lúcia M F S; Rocha, Fábio R P

    2015-11-01

    Formaldehyde is often added to foods as a preservative, but it is highly toxic to humans, having been identified as a carcinogenic substance. It has also been used for the adulteration of milk in order to diminish the bacteria count and increase the shelf life of the product. Herein, we present a green dispersive liquid-liquid microextraction procedure in a flow-batch system for the determination of formaldehyde in milk. Pulsed flows were exploited for the first time to improve the dispersion of the extractant in the aqueous phase. The Hantzsch reaction was used for the derivatization of formaldehyde and the product was extracted with the ionic liquid (IL) trihexyltetradecylphosphonium chloride with methanol as the disperser. The flow-batch chamber was made of stainless steel with the facility for resistive heating to speed up the derivatization reaction. Spectrophotometric measurements were directly carried out in the organic phase using an optical fiber spectrophotometer. The limit of detection and coefficient of variation were 100 μg L(-1) and 3.1% (n=10), respectively, with a linear response from 0.5 to 5.0 mg L(-1), described by the equation A=0.088+0.116CF (mg L(-1)) in which A is absorbance and CF is formaldehyde concentration in mg L(-1). The estimated recoveries of formaldehyde from spiked milk samples ranged from 91% to 106% and the slopes of the analytical curves obtained with reference solutions in water or milk were in agreement, thus indicating the absence of matrix effects. Accuracy was demonstrated by the agreement of the results with those achieved by the reference fluorimetric procedure at the 95% confidence level. The proposed procedure allows for 10 extractions per hour, with minimized reagent consumption (120 μL of IL and 3.5 μL acetylacetone) and generation of only 6.7 mL waste per determination, which contribute to the eco-friendliness of the procedure.

  4. Determination of formaldehyde levels in 100 furniture workshops in Ankara.

    PubMed

    Vaizoğlu, Songül Acar; Aycan, Sefer; Akin, Levent; Koçdor, Pelin; Pamukçu, Gül; Muhsinoğlu, Orkun; Ozer, Feyza; Evci, E Didem; Güler, Cağatay

    2005-10-01

    One of the airborne pollutants in wood products industry is formaldehyde, which may pose some health effects. Therefore this study is conducted to determine formaldehyde levels in 100 furniture-manufacturing workshops in Ankara and also to determine the symptoms, which may be related with formaldehyde exposure among the workers. Indoor formaldehyde levels ranged from 0.02 ppm to 2.22 ppm with a mean of 0.6 +/- 0.3 ppm. Outdoor formaldehyde levels also ranged from 0.0 ppm to 0.08 ppm with a mean of 0.03 +/- 0.03 ppm. Formaldehyde levels were higher in workplaces located at basement than in workplaces located at or above ground level (p < 0.01). An association was found between indoor formaldehyde levels and the types of fuel used (p < 0.05). The levels were higher in workplaces where only sawdust was used for heating, than in workplaces where wood, coal, and sawdust are used (p = 0.02). An association was found between runny nose and indoor formaldehyde levels (p = 0.03). Formaldehyde levels were lower in workplaces where employees had no symptoms than in those where employees had 4 or more symptoms (p = 0.02). Of 229 employees 57 subjects (24.9%) work under the formaldehyde levels of 0.75 ppm and above. Thus, approximately one fourth of the employees in workplaces are working in environments with formaldehyde levels exceeding those permitted by Occupational Safety and Health Administration (OSHA). The employees working in small-scale furniture workshops are at risk of formaldehyde exposure. Measures, such as improved ventilation, have to be taken in these workplaces, in order to decrease the formaldehyde levels.

  5. 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...

  6. OTEC energy via methanol production

    SciTech Connect

    Avery, W.H.; Richards, D.; Niemeyer, W.G.; Shoemaker, J.D.

    1983-01-01

    The conceptual design of an 160 MW/sub e/ OTEC plantship has been documented; it is designed to produce 1000 tonne/day of fuel-grade methanol from coal slurry shipped to the plantship, using oxygen and hydrogen from the on-board electrolysis of water. Data and components are used that were derived by Brown and Root Development, Inc. (BARDI) in designing a barge-mounted plant to make methanol from natural gas for Litton Industries and in the design and construction of a coal-to-ammonia demonstration plant in operation at Muscle Shoals, Alabama, for the Tennessee Valley Authority (TVA). The OTEC-methanol plant design is based on the use of the Texaco gasifier and Lurgi synthesis units. The sale price of OTEC methanol delivered to port from this first-of-a-kind plant is estimated to be marginally competitive with methanol from other sources at current market prices.

  7. The microcapsule-type formaldehyde scavenger: the preparation and the application in urea-formaldehyde adhesives.

    PubMed

    Duan, Hongyun; Qiu, Teng; Guo, Longhai; Ye, Jun; Li, Xiaoyu

    2015-08-15

    The limitation and regulation of formaldehyde emissions (FE) now shows great importance in wood-based materials such as plywood and particle board manufactured for building and furnishing materials. The widely used formaldehyde-based adhesives are one of the main sources of FE from the wood products. In this work, a new kind of long-term effective formaldehyde scavenger in the microcapsule form was prepared by using an intra-liquid desiccation method. The characterizations of the capsule (UC) were performed including the morphologies, the yields, the loading efficiency as well as its sustained-release of urea in aqueous conditions. The prepared UC could be integrated in urea-formaldehyde resins by simply physical blending, and the mixtures were available to be applied as the adhesives for the manufacture of plywood. The bonding strength (BS) and the FE of the bonded plywood in both short (3h) and long (12 week) period were evaluated in detail. It was found that the FE profile of the plywood behaved following a duple exponential law within 12 week. The addition of UC in the adhesive can effectively depress the FE of the plywood not only in a short period after preparation but also in a long-term period during its practical application. The slow released urea would continuously suppress the emission of toxic formaldehyde in a sustained manner without obviously deteriorating on the BS of the adhesives.

  8. Recombinant protein expression in Pichia pastoris strains with an engineered methanol utilization pathway

    PubMed Central

    2012-01-01

    Βackground The methylotrophic yeast Pichia pastoris has become an important host organism for recombinant protein production and is able to use methanol as a sole carbon source. The methanol utilization pathway describes all the catalytic reactions, which happen during methanol metabolism. Despite the importance of certain key enzymes in this pathway, so far very little is known about possible effects of overexpressing either of these key enzymes on the overall energetic behavior, the productivity and the substrate uptake rate in P. pastoris strains. Results A fast and easy-to-do approach based on batch cultivations with methanol pulses was used to characterize different P. pastoris strains. A strain with MutS phenotype was found to be superior over a strain with Mut+ phenotype in both the volumetric productivity and the efficiency in expressing recombinant horseradish peroxidase C1A. Consequently, either of the enzymes dihydroxyacetone synthase, transketolase or formaldehyde dehydrogenase, which play key roles in the methanol utilization pathway, was co-overexpressed in MutS strains harboring either of the reporter enzymes horseradish peroxidase or Candida antarctica lipase B. Although the co-overexpression of these enzymes did not change the stoichiometric yields of the recombinant MutS strains, significant changes in the specific growth rate, the specific substrate uptake rate and the specific productivity were observed. Co-overexpression of dihydroxyacetone synthase yielded a 2- to 3-fold more efficient conversion of the substrate methanol into product, but also resulted in a reduced volumetric productivity. Co-overexpression of formaldehyde dehydrogenase resulted in a 2-fold more efficient conversion of the substrate into product and at least similar volumetric productivities compared to strains without an engineered methanol utilization pathway, and thus turned out to be a valuable strategy to improve recombinant protein production. Conclusions Co

  9. Silver as acrolein hydrogenation catalyst: intricate effects of catalyst nature and reactant partial pressures.

    PubMed

    Bron, Michael; Teschner, Detre; Knop-Gericke, Axel; Jentoft, Friederike C; Kröhnert, Jutta; Hohmeyer, Jens; Volckmar, Claudia; Steinhauer, Bernd; Schlögl, Robert; Claus, Peter

    2007-07-21

    The hydrogenation of acrolein over pure and supported silver has been investigated with a focus on the influence of catalyst structure and reaction pressure (mbar to 20 bar range) on activity and selectivity. An onset of formation of allyl alcohol beyond 100 mbar reaction pressure (at 250 degrees C) is ascribed to a change in adsorption geometry upon increasing coverage. Smaller silver particles (in the nanometer range), the proximity of a reducible oxide component as well as high pressure lead to enhanced allyl alcohol formation; the selectivity to the other main product propionaldehyde is reduced. The silver dispersion changed depending on the reaction pressure. Moreover, the presence of oxygen, most likely as subsurface oxygen, and the presence of defects are of paramount importance for the catalytic behaviour. The considerable changes of the silver catalysts under reaction conditions and the pressure dependence call for in situ measurements to establish true structure-activity/selectivity relationships for this system. PMID:17612721

  10. 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

  11. The active component of vanadium-molybdenum catalysts for the oxidation of acrolein to acrylic acid

    SciTech Connect

    Andrushkevich, T.V.; Kuznetsova, T.G.

    1986-12-01

    The catalytic properties of the vanadium-molybdenum oxide system were investigated in the oxidation of acrolein to acrylic acid. The active component of the catalyst is the compound VMo/sub 3/O/sub 11/, the maximum amount of which is observed at a content of 7-15 mole% V/sub 2/O/sub 4/. The compound VMo/sub 3/O/sub 11/ is formed in the thermodecomposition of silicomolybdovanadium heteropoly acids or isopoly compounds, reduced with respect to vanadium, and contains V/sup 4 +/ and Mo/sup 6 +/. The optimum treatment for the formation of this compound is treatment in the reaction mixture at 400 degrees C.

  12. Support effect in oxide catalysis: methanol oxidation on vanadia/ceria.

    PubMed

    Kropp, Thomas; Paier, Joachim; Sauer, Joachim

    2014-10-15

    Density functional theory is used for periodic models of monomeric vanadia species deposited on the CeO2(111) surface to study dissociative adsorption of methanol and its subsequent dehydrogenation to formaldehyde. Dispersion-corrected PBE+U calculations are performed and compared with HSE and B3LYP results. Dissociative adsorption of methanol at different sites on VO2·CeO2(111) is highly exothermic with adsorption energies of 1.8 to 1.9 eV (HSE+D). Two relevant pathways for desorption of formaldehyde are found with intrinsic barriers for the redox step of 1.0 and 1.4 eV (HSE+D). The calculated desorption temperatures (370 and 495 K) explain the peaks observed in temperature-programmed desorption experiments. Different sites of the supported catalyst system are involved in the two pathways: (i) methanol can chemisorb on the CeO2 surface filling a so-called pseudovacancy and the H atom is transferred to an V-O-Ce interphase bond or (ii) CH3OH may chemisorb at the V-O-Ce interphase bond and form a V-OCH3 species from which H is transferred to the ceria surface, providing evidence for true cooperativity. In both cases, ceria is directly involved in the redox process, as two electrons are accommodated in Ce f states forming two Ce(3+) ions whereas vanadium remains fully oxidized (V(5+)). PMID:25275568

  13. Photocatalytic chemistry of methanol on rutile TiO₂(011)-(2 × 1).

    PubMed

    Wang, Zhiqiang; Hao, Qunqing; Mao, Xinchun; Zhou, Chuanyao; Dai, Dongxu; Yang, Xueming

    2016-04-21

    Photocatalytic chemistry of methanol on the reconstructed rutile TiO2(011)-(2 × 1) surface upon 266 nm and 400 nm light excitation has been investigated quantitatively using the post-irradiation temperature-programmed desorption (TPD) method. Photochemical products such as formaldehyde, methyl formate and water, which result from the recombination of surface bridging hydroxyls through the abstraction of lattice oxygen atoms, have been identified under both 266 nm and 400 nm light irradiation. However, ethylene is detected only under 266 nm light irradiation. Through an analogy experiment, ethylene production is attributed to the photochemistry and the following thermochemistry of formaldehyde. The absence of the ethylene signal under 400 nm light is consistent with the significantly lower conversion at this wavelength compared with 266 nm. The photocatalytic reaction rate of methanol is also wavelength dependent. Possible reasons for the photon energy dependent phenomena have been discussed. This work not only provides a detailed characterization of the photochemistry of methanol on the rutile TiO2(011)-(2 × 1) surface, but also indicates the importance of photon energy in the photochemistry on TiO2 surfaces. PMID:27020321

  14. California methanol assessment. Volume 1: Summary report

    NASA Technical Reports Server (NTRS)

    Otoole, R.; Dutzi, E.; Gershman, R.; Heft, R.; Kalema, W.; Maynard, D.

    1983-01-01

    The near term methanol industry, the competitive environment, long term methanol market, the transition period, air quality impacts of methanol, roles of the public and private sectors are considered.

  15. A combined experimental and computational study of the catalytic dehydration of glycerol on microporous zeolites: an investigation of the reaction mechanism and acrolein selectivity.

    PubMed

    Lin, Xufeng; Lv, Yanhong; Qu, Yuanyuan; Zhang, Guodong; Xi, Yanyan; Phillips, David L; Liu, Chenguang

    2013-12-14

    The catalytic activity and the acrolein selectivity for liquid phase glycerol dehydration on β zeolites (HNa-β-k) were found to be dependent on the reaction temperature as well as on the amount of acid sites on the zeolites. An increase in the reaction temperature favors the acrolein selectivity. The acrolein selectivity increases with the Na(+)/H(+) ratio and the glycerol conversion decreases with it so that a maximum acrolein yield is obtained when a certain amount of acidic sites are replaced by non-active Na(+) sites. The computational results indicate that 3-hydoxylpropanal (HPA) is an important intermediate that determines the final product selectivity. The relative rates of the different reaction pathways for HAP can be affected by the amount of water molecules involved in its homogeneous reaction. Based on the reaction mechanism proposed, it was hypothesized that smaller pores reduce activity but increase selectivity to acrolein, and results of the H-MFI zeolite were consistent with this hypothesis. Our work provides important insight into the overall landscape of the reaction mechanism and can be used to help design reaction systems that have good acrolein selectivity for the liquid phase glycerol dehydration reactions.

  16. NMR investigation of acrolein stability in hydroalcoholic solution as a foundation for the valid HS-SPME/GC-MS quantification of the unsaturated aldehyde in beverages.

    PubMed

    Kächele, Martin; Monakhova, Yulia B; Kuballa, Thomas; Lachenmeier, Dirk W

    2014-04-11

    Acrolein (propenal) is found in many foods and beverages and may pose a health hazard due to its cytotoxicity. Considerable knowledge gaps regarding human exposure to acrolein exist, and there is a lack of reliable analytical methods. Hydroalcoholic dilutions prepared for calibration purposes from pure acrolein show considerable degradation of the compound and nuclear magnetic resonance (NMR) spectroscopy showed that 1,3,3-propanetriol and 3-hydroxypropionaldehyde are formed. The degradation can be prevented by addition of hydroquinone as stabilizer to the calibration solutions, which then show linear concentration-response behaviour required for quantitative analysis. The stabilized calibration solutions were used for quantitative headspace solid-phase microextraction/gas chromatography-mass spectrometry (HS-SPME/GC-MS) determination of acrolein in alcoholic beverages with a detection limit of 14 μg L(-1). Of 117 tested alcoholic beverages, 64 were tested positive with the highest incidence in grape marc spirits and whiskey (100%, mean 252 μg L(-1)), followed by fruit spirits (86%, mean 591 μg/L(-1)), tequila (86%, mean 404 μg L(-1)), Asian spirits (43%, mean 54 μg L(-1)) and wine (9%, mean 0.7 μg L(-1)). Acrolein could not be detected in beer, vodka, absinthe and bottled water. Six of the fruit and grape marc spirits had acrolein levels above the World Health Organization (WHO) provisional tolerable concentration of 1.5 mg L(-1).

  17. NMR investigation of acrolein stability in hydroalcoholic solution as a foundation for the valid HS-SPME/GC-MS quantification of the unsaturated aldehyde in beverages.

    PubMed

    Kächele, Martin; Monakhova, Yulia B; Kuballa, Thomas; Lachenmeier, Dirk W

    2014-04-11

    Acrolein (propenal) is found in many foods and beverages and may pose a health hazard due to its cytotoxicity. Considerable knowledge gaps regarding human exposure to acrolein exist, and there is a lack of reliable analytical methods. Hydroalcoholic dilutions prepared for calibration purposes from pure acrolein show considerable degradation of the compound and nuclear magnetic resonance (NMR) spectroscopy showed that 1,3,3-propanetriol and 3-hydroxypropionaldehyde are formed. The degradation can be prevented by addition of hydroquinone as stabilizer to the calibration solutions, which then show linear concentration-response behaviour required for quantitative analysis. The stabilized calibration solutions were used for quantitative headspace solid-phase microextraction/gas chromatography-mass spectrometry (HS-SPME/GC-MS) determination of acrolein in alcoholic beverages with a detection limit of 14 μg L(-1). Of 117 tested alcoholic beverages, 64 were tested positive with the highest incidence in grape marc spirits and whiskey (100%, mean 252 μg L(-1)), followed by fruit spirits (86%, mean 591 μg/L(-1)), tequila (86%, mean 404 μg L(-1)), Asian spirits (43%, mean 54 μg L(-1)) and wine (9%, mean 0.7 μg L(-1)). Acrolein could not be detected in beer, vodka, absinthe and bottled water. Six of the fruit and grape marc spirits had acrolein levels above the World Health Organization (WHO) provisional tolerable concentration of 1.5 mg L(-1). PMID:24745744

  18. Modification by acrolein, a component of tobacco smoke and age-related oxidative stress, mediates functional impairment of human apolipoprotein E.

    PubMed

    Tamamizu-Kato, Shiori; Wong, Jason Yiu; Jairam, Vikram; Uchida, Koji; Raussens, Vincent; Kato, Hiroyuki; Ruysschaert, Jean-Marie; Narayanaswami, Vasanthy

    2007-07-17

    Oxidative damage to proteins such as apolipoprotein B-100 increases the atherogenicity of low-density lipoproteins (LDL). However, little is known about the potential oxidative damage to apolipoprotein E (apoE), an exchangeable antiatherogenic apolipoprotein. ApoE plays an integral role in lipoprotein metabolism by regulating the plasma cholesterol and triglyceride levels. Hepatic uptake of lipoproteins is facilitated by apoE's ability to bind with cell surface heparan sulfate proteoglycans and to lipoprotein receptors via basic residues in its 22 kDa N-terminal domain (NT). We investigated the effect of acrolein, an aldehydic product of endogenous lipid peroxidation and a tobacco smoke component, on the conformation and function of recombinant human apoE3-NT. Acrolein caused oxidative modification of apoE3-NT as detected by Western blot with acrolein-lysine-specific antibodies, and tertiary conformational alterations. Acrolein modification impairs the ability of apoE3-NT to interact with heparin and the LDL receptor. Furthermore, acrolein-modified apoE3-NT displayed a 5-fold decrease in its ability to interact with lipid surfaces. Our data indicate that acrolein disrupts the functional integrity of apoE3, which likely interferes with its role in regulating plasma cholesterol homeostasis. These observations have implications regarding the role of apoE in the pathogenesis of smoking- and oxidative stress-mediated cardiovascular and cerebrovascular diseases.

  19. Electronic excitations in a dielectric continuum solvent with quantum Monte Carlo: Acrolein in water

    NASA Astrophysics Data System (ADS)

    Floris, Franca Maria; Filippi, Claudia; Amovilli, Claudio

    2014-01-01

    We investigate here the vertical n → π* and π → π* transitions of s-trans-acrolein in aqueous solution by means of a polarizable continuum model (PCM) we have developed for the treatment of the solute at the quantum Monte Carlo (QMC) level of the theory. We employ the QMC approach which allows us to work with highly correlated electronic wave functions for both the solute ground and excited states and, to study the vertical transitions in the solvent, adopt the commonly used scheme of considering fast and slow dielectric polarization. To perform calculations in a non-equilibrium solvation regime for the solute excited state, we add a correction to the global dielectric polarization charge density, obtained self consistently with the solute ground-state wave function by assuming a linear-response scheme. For the solvent polarization in the field of the solute in the ground state, we use the static dielectric constant while, for the electronic dielectric polarization, we employ the solvent refractive index evaluated at the same frequency of the photon absorbed by the solute for the transition. This choice is shown to be better than adopting the most commonly used value of refractive index measured in the region of visible radiation. Our QMC calculations show that, for standard cavities, the solvatochromic shifts obtained with the PCM are underestimated, even though of the correct sign, for both transitions of acrolein in water. Only by reducing the size of the cavity to values where more than one electron is escaped to the solvent region, we regain the experimental shift for the n → π* case and also improve considerably the shift for the π → π* transition.

  20. Electronic excitations in a dielectric continuum solvent with quantum Monte Carlo: Acrolein in water

    SciTech Connect

    Floris, Franca Maria Amovilli, Claudio; Filippi, Claudia

    2014-01-21

    We investigate here the vertical n → π{sup *} and π → π{sup *} transitions of s-trans-acrolein in aqueous solution by means of a polarizable continuum model (PCM) we have developed for the treatment of the solute at the quantum Monte Carlo (QMC) level of the theory. We employ the QMC approach which allows us to work with highly correlated electronic wave functions for both the solute ground and excited states and, to study the vertical transitions in the solvent, adopt the commonly used scheme of considering fast and slow dielectric polarization. To perform calculations in a non-equilibrium solvation regime for the solute excited state, we add a correction to the global dielectric polarization charge density, obtained self consistently with the solute ground-state wave function by assuming a linear-response scheme. For the solvent polarization in the field of the solute in the ground state, we use the static dielectric constant while, for the electronic dielectric polarization, we employ the solvent refractive index evaluated at the same frequency of the photon absorbed by the solute for the transition. This choice is shown to be better than adopting the most commonly used value of refractive index measured in the region of visible radiation. Our QMC calculations show that, for standard cavities, the solvatochromic shifts obtained with the PCM are underestimated, even though of the correct sign, for both transitions of acrolein in water. Only by reducing the size of the cavity to values where more than one electron is escaped to the solvent region, we regain the experimental shift for the n → π{sup *} case and also improve considerably the shift for the π → π{sup *} transition.

  1. Vapor Phase Dehydration of Glycerol to Acrolein Over SBA-15 Supported Vanadium Substituted Phosphomolybdic Acid Catalyst.

    PubMed

    Viswanadham, Balaga; Srikanth, Amirineni; Kumar, Vanama Pavan; Chary, Komandur V R

    2015-07-01

    Vapor phase dehydration of glycerol to acrolein was investigated over heteropolyacid (HPA) catalysts containing vanadium substituted phosphomolybdic acid (H4PMo11VO40) supported on mesoporous SBA-15. A series of HPA catalysts with HPA loadings varying from 10-50 wt% were prepared by impregnation method on SBA-15 support. The catalysts were characterized by X-ray diffraction, Raman spectroscopy, Fourier Transform infrared spectroscopy, temperature-programmed desorption of NH3, pyridine adsorbed FT-IR spectroscopy, scanning electron microscopy, pore size distribution and specific surface area measurements. The nature of acidic sites was examined by pyridine adsorbed FT-IR spectroscopy. XRD results suggest that the active phase containing HPA was highly dispersed at lower loadings on the support. FT-IR and Raman spectra results confirm that the presence of primary Keggin ion structure of HPA on the support and it was not affected during the preparation of catalysts. Pore size distribution results reveal that all the samples show unimodel pore size distribution with well depicted mesoporous structure. NH3-TPD results suggest that the acidity of catalysts increased with increase of HPA loading. The findings of acidity measurements by FT-IR spectra of pyridine adsorption reveals that the catalysts consist both the Brønsted and Lewis acidic sites and the amount of Brønsted acidic sites are increasing with HPA loading. SBA-15 supported vanadium substituted phosphomolybdic acid catalysts are found to be highly active during the dehydration reaction and exhibited 100% conversion of glycerol (10 wt% of glycerol) and the acrolein selectivity was appreciably changed with HPA active phase loading. The catalytic functionalities during glycerol dehydration are well correlated with surface acidity of the catalysts.

  2. Electronic excitations in a dielectric continuum solvent with quantum Monte Carlo: acrolein in water.

    PubMed

    Floris, Franca Maria; Filippi, Claudia; Amovilli, Claudio

    2014-01-21

    We investigate here the vertical n → π(*) and π → π(*) transitions of s-trans-acrolein in aqueous solution by means of a polarizable continuum model (PCM) we have developed for the treatment of the solute at the quantum Monte Carlo (QMC) level of the theory. We employ the QMC approach which allows us to work with highly correlated electronic wave functions for both the solute ground and excited states and, to study the vertical transitions in the solvent, adopt the commonly used scheme of considering fast and slow dielectric polarization. To perform calculations in a non-equilibrium solvation regime for the solute excited state, we add a correction to the global dielectric polarization charge density, obtained self consistently with the solute ground-state wave function by assuming a linear-response scheme. For the solvent polarization in the field of the solute in the ground state, we use the static dielectric constant while, for the electronic dielectric polarization, we employ the solvent refractive index evaluated at the same frequency of the photon absorbed by the solute for the transition. This choice is shown to be better than adopting the most commonly used value of refractive index measured in the region of visible radiation. Our QMC calculations show that, for standard cavities, the solvatochromic shifts obtained with the PCM are underestimated, even though of the correct sign, for both transitions of acrolein in water. Only by reducing the size of the cavity to values where more than one electron is escaped to the solvent region, we regain the experimental shift for the n → π(*) case and also improve considerably the shift for the π → π(*) transition.

  3. Problems associated with the use of urea-formaldehyde foam for residential insulation. Part II. The effects of temperature and humidity on free formaldehyde, extractable formaldehyde, formaldehyde emission, and physical characteristics of the foam

    SciTech Connect

    Schutte, W.C.; Cole, R.S.; Frank, C.W.; Long, K.R.

    1981-02-01

    Results of testing with two products of urea-formaldehyde based foams are described. Results of three products have previously been reported. Methods for detection and quantitative determination of formaldehyde, design of the experimental chambers, and the procedures are described. Samples of Product D were monitored for about 29 days and samples of Product E were monitored for 60 days in chambers and results are tabulated for formaldehyde emission. Additional tests performed on the two products are: extractable formaldehyde (high and low temperature conditions); free formaldehyde (high and low temperature conditions); comparison of free formaldehyde concentration; density (high and low temperature conditions); shrinkage (high and low temperature conditions). Control panels were constructed to simulate a wall in a home and observations were made and compared with results of the experimental products.

  4. A rapid liquid chromatography determination of free formaldehyde in cod.

    PubMed

    Storey, Joseph M; Andersen, Wendy C; Heise, Andrea; Turnipseed, Sherri B; Lohne, Jack; Thomas, Terri; Madson, Mark

    2015-01-01

    A rapid method for the determination of free formaldehyde in cod is described. It uses a simple water extraction of formaldehyde which is then derivatised with 2,4-dinitrophenylhydrazine (DNPH) to form a sensitive and specific chromophore for high-performance liquid chromatography (HPLC) detection. Although this formaldehyde derivative has been widely used in past tissue analysis, this paper describes an improved derivatisation procedure. The formation of the DNPH formaldehyde derivative has been shortened to 2 min and a stabilising buffer has been added to the derivative to increase its stability. The average recovery of free formaldehyde in spiked cod was 63% with an RSD of 15% over the range of 25-200 mg kg(-1) (n = 48). The HPLC procedure described here was also compared to a commercial qualitative procedure - a swab test for the determination of free formaldehyde in fish. Several positive samples were compared by both methods.

  5. Ambient air measurement of acrolein and other carbonyls at the Oakland-San Francisco Bay Bridge toll plaza.

    PubMed

    Destaillats, Hugo; Spaulding, Reggie S; Charles, M Judith

    2002-05-15

    Interest in ambient concentrations of acrolein and other alpha,beta-unsaturated aldehydes and dicarbonyls (e.g., crotonaldehyde, methyl glyoxal, glyoxal, malonaldehyde (malondialdehyde)) is growing because either they exist at high levels in motor vehicle emissions or they arise from photooxidation of other hydrocarbons emitted from mobile sources. In addition, their mutagenic, genotoxic, or carcinogenic properties are well-established, and the results of a dispersion-modeling study regarding the health risks posed by the 188 hazardous air pollutants in California attributes the highest noncancer risk to exposure to acrolein. Such modeling studies, conducted by the U.S. Environmental Protection Agency (U.S. EPA), also predict median ambient air concentrations of acrolein higher than 0.06 microg/m3, the chronic inhalation reference exposure level stipulated by the California Office of Environmental Health Hazard Assessment in counties surrounding the Oakland-San Francisco Bay Bridge. We measured acrolein and other potentially toxic carbonyls in air sampled at the San Francisco Bay Bridge toll plaza during rush hour traffic, which may be considered a "worst case scenario" for outdoor airborne carbonyls. We identified 36 carbonyls in the sample extracts, including 14 saturated aliphatic carbonyls, six unsaturated carbonyls, four aromatic carbonyls, six dicarbonyls, and six hydroxy carbonyls. Structural information to support tentative identification of carbonyls and hydroxycarbonyls was obtained by using a method that involves O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and PFBHA/bis(trimethylsilyl)trifluoroacetamide (BSTFA) derivatization in concert with gas chromatography/ion trap mass spectrometry. Most notably, we report for the first time the presence of malonaldehyde in the ambient atmospheric environment. A relatively linear relationship between retention time and the molecular weight of the derivatives was established to assist in obtaining structural

  6. Determination of Formaldehyde in Cigarette Smoke

    NASA Astrophysics Data System (ADS)

    Wong, Jon W.; Ngim, Kenley K.; Eiserich, Jason P.; Yeo, Helen C. H.; Shibamoto, Takayuki; Mabury, Scott A.

    1997-09-01

    Formaldehdye is considered a hazardous air pollutant with numerous sources that include environmental tobacco smoke (ETS). With the increasing interest regarding ETS and public health the measurement of formaldehyde readily lends itself to a laboratory experiment comparing methods of analysis. This experiment involves the collection, derivatization, extraction, and analysis of formaldehyde from cigarette smoke using two methods. Formaldehyde is extracted from smoke and derivitized with a solution of 2,4-DNPH with subsequent cleanup by solid-phase extraction and analysis of the hydrazone by HPLC with UV detection; additionally a solution of cysteamine yields the corresponding thiazolidine derivative that is liquid/liquid extracted and subsequently analyzed by either GC with NPD or FPD (sulfur mode). Reasonable agreement among the methods was obtained by lab demonstrators with spike recoveries yielding 94.7 + 6.8 (n=5) and 89.2 (n = 4) % for NPD and FPD, respectively while HPLC spiked recoveries were 83.6 + 3.2 (n = 5) %; mean class spike recoveries ranged from 80-100%. Student results (in mg/cigarette) from smoke samples were similar to literature values with 163.2 + 69.2 (n = 7) and 149.4 (n = 7) % for NPD and FPD, respectively; the HPLC result was significantly lower at 45.1 + 23.7(n = 7) with losses presumably due to hydrazone precipitating from the smoke extracted solution. Students particularly benefited from the "real world" nature of the analysis and the experience evaluating disparate methods of determining a common analyte.

  7. Human performance during experimental formaldehyde exposure

    SciTech Connect

    Bach, B.; Pedersen, O.F.; Moelhave, L. )

    1990-01-01

    Sixty-one subjects were exposed in a climate chamber for 5.5 hours to a controlled atmospheric environment. Formaldehyde vapors were added in concentrations of 0, 0.15, 0.40, or 1.20 mg/m{sup 3}. The exposures were arranged in a 4 x 4, balanced latin square design, involving four days in each of four weeks. The subjects were all males. Of these 32 had occupational exposure to formaldehyde in industrial productions of than five years. Twenty-nine were randomly selected, matched controls from the normal population. The hypothesis tested was that significant, but different dose-response relations exist in a number of performance tests for these two groups of subjects. The results indicate such differences in reactions to tests of short term memory and ability to concentrate (digit span tests, digit symbol test, graphic continuous performance test) and an addition test. Whether these results indicate chronic or acute CNS effects or they are caused by distractive sensory irritation due to formaldehyde exposure is discussed.

  8. Indoor formaldehyde removal over CMK-3

    PubMed Central

    2012-01-01

    The removal of formaldehyde at low concentrations is important in indoor air pollution research. In this study, mesoporous carbon with a large specific surface area was used for the adsorption of low-concentration indoor formaldehyde. A mesoporous carbon material, CMK-3, was synthesized using the nano-replication method. SBA-15 was used as a mesoporous template. The surface of CMK-3 was activated using a 2N H2SO4 solution and NH3 gas to prepare CMK-3-H2SO4 and CMK-3-NH3, respectively. The activated samples were characterized by N2 adsorption-desorption, X-ray diffraction, and X-ray photoelectron spectroscopy. The formaldehyde adsorption performance of the mesoporous carbons was in the order of CMK-3-NH3 > CMK-3-H2SO4 > CMK-3. The difference in the adsorption performance was explained by oxygen and nitrogen functional groups formed during the activation process and by the specific surface area and pore structure of mesoporous carbon. PMID:22221425

  9. Thermal and photochemical reactions of methanol on nanocrystalline anatase TiO2 thin films.

    PubMed

    Bennett, David A; Cargnello, Matteo; Gordon, Thomas R; Murray, Christopher B; Vohs, John M

    2015-07-14

    The catalytic and photo-catalytic activity of well-defined anatase TiO2 nanocrystals for the partial oxidation of methanol was investigated using temperature-programmed desorption (TPD) in ultra-high vacuum in order to determine how crystallite size and shape affect reactivity. The TiO2 films used in this study were prepared from well-defined TiO2 nanocrystals synthesized by colloidal methods. These nanocrystals had a truncated bi-pyramidal shape which exposes primarily (101) and to a lesser extent (001) surfaces and ranged in size from 10 to 25 nm. Two distinct regimes of reactivity were investigated, namely in the dark and under UV light illumination. In the dark, methanol adsorbed dissociatively on the (001) planes and only molecularly on the (101) surfaces. Dissociated methoxy groups on the (001) surfaces coupled to produce dimethyl ether, suggesting the presence of fourfold coordinate Ti cations. Under UV light illumination, the nanocrystals were additionally found to be active for the photo-catalytic oxidation of methanol to methyl formate. On the (101) surfaces, this reaction proceeded in a stepwise photocatalytic pathway involving dehydrogenation of methanol to form methoxy groups and then formaldehyde, followed by coupling of these latter two species to form methyl formate. The (001) surfaces were also found to be photo-catalytically active but surface methoxy groups could be produced thermally and the reaction proceeds only to formaldehyde in the absence of molecularly adsorbed methanol. The overall photocatalytic activity of the nanocrystals was also was found to increase with increasing crystallite size. The results of this study show that thin films of well-defined nanocrystals are excellent model systems that can be used to help bridge the materials gap between studies of single crystal surfaces and high surface area polycrystalline catalysts. PMID:26073428

  10. Formaldehyde-negative allergic contact dermatitis from melamine-formaldehyde resin.

    PubMed

    Aalto-Korte, K; Jolanki, R; Estlander, T

    2003-10-01

    Melamine-formaldehyde resin (MFR) is used as a textile finish, in tableware, in surface coatings, and in glues in the furniture and wood industry. MFR is considered to be an infrequent sensitizer. Contact allergy to MFR is often combined with formaldehyde allergy. Patients allergic to textile finish often react to MFR, although other finishes are nowadays more commonly used. Besides allergy to textile finish, allergic contact dermatitis from MFR has been described in workers in composite production and in an orthopaedic plaster technician. To our knowledge, there are no previous reports of contact allergy in the plywood industry from MFR. We describe 3 cases of occupational allergic contact dermatitis from MFR without contact allergy to formaldehyde, 1 in the plywood industry, 1 in the production of melamine-laminated chipboard and 1 in laboratory work.

  11. Formaldehyde scavengers function as novel antigen retrieval agents.

    PubMed

    Vollert, Craig T; Moree, Wilna J; Gregory, Steven; Bark, Steven J; Eriksen, Jason L

    2015-11-27

    Antigen retrieval agents improve the detection of formaldehyde-fixed proteins, but how they work is not well understood. We demonstrate that formaldehyde scavenging represents a key characteristic associated with effective antigen retrieval; under controlled temperature and pH conditions, scavenging improves the typical antigen retrieval process through reversal of formaldehyde-protein adduct formation. This approach provides a rational framework for the identification and development of more effective antigen retrieval agents.

  12. Formaldehyde scavengers function as novel antigen retrieval agents

    PubMed Central

    Vollert, Craig T.; Moree, Wilna J.; Gregory, Steven; Bark, Steven J.; Eriksen, Jason L.

    2015-01-01

    Antigen retrieval agents improve the detection of formaldehyde-fixed proteins, but how they work is not well understood. We demonstrate that formaldehyde scavenging represents a key characteristic associated with effective antigen retrieval; under controlled temperature and pH conditions, scavenging improves the typical antigen retrieval process through reversal of formaldehyde-protein adduct formation. This approach provides a rational framework for the identification and development of more effective antigen retrieval agents. PMID:26612041

  13. BLM protein mitigates formaldehyde-induced genomic instability.

    PubMed

    Kumari, Anuradha; Owen, Nichole; Juarez, Eleonora; McCullough, Amanda K

    2015-04-01

    Formaldehyde is a reactive aldehyde that has been classified as a class I human carcinogen by the International Agency for Cancer Research. There are growing concerns over the possible adverse health effects related to the occupational and environmental human exposures to formaldehyde. Although formaldehyde-induced DNA and protein adducts have been identified, the genomic instability mechanisms and the cellular tolerance pathways associated with formaldehyde exposure are not fully characterized. This study specifically examines the role of a genome stability protein, Bloom (BLM) in limiting formaldehyde-induced cellular and genetic abnormalities. Here, we show that in the absence of BLM protein, formaldehyde-treated cells exhibited increased cellular sensitivity, an immediate cell cycle arrest, and an accumulation of chromosome radial structures. In addition, live-cell imaging experiments demonstrated that formaldehyde-treated cells are dependent on BLM for timely segregation of daughter cells. Both wild-type and BLM-deficient formaldehyde-treated cells showed an accumulation of 53BP1 and γH2AX foci indicative of DNA double-strand breaks (DSBs); however, relative to wild-type cells, the BLM-deficient cells exhibited delayed repair of formaldehyde-induced DSBs. In response to formaldehyde exposure, we observed co-localization of 53BP1 and BLM foci at the DSB repair site, where ATM-dependent accumulation of formaldehyde-induced BLM foci occurred after the recruitment of 53BP1. Together, these findings highlight the significance of functional interactions among ATM, 53BP1, and BLM proteins as responders associated with the repair and tolerance mechanisms induced by formaldehyde.

  14. Dietary Methanol Regulates Human Gene Activity

    PubMed Central

    Komarova, Tatiana V.; Sheshukova, Ekaterina V.; Kosorukov, Vyacheslav S.; Kiryanov, Gleb I.; Dorokhov, Yuri L.

    2014-01-01

    Methanol (MeOH) is considered to be a poison in humans because of the alcohol dehydrogenase (ADH)-mediated conversion of MeOH to formaldehyde (FA), which is toxic. Our recent genome-wide analysis of the mouse brain demonstrated that an increase in endogenous MeOH after ADH inhibition led to a significant increase in the plasma MeOH concentration and a modification of mRNA synthesis. These findings suggest endogenous MeOH involvement in homeostasis regulation by controlling mRNA levels. Here, we demonstrate directly that study volunteers displayed increasing concentrations of MeOH and FA in their blood plasma when consuming citrus pectin, ethanol and red wine. A microarray analysis of white blood cells (WBC) from volunteers after pectin intake showed various responses for 30 significantly differentially regulated mRNAs, most of which were somehow involved in the pathogenesis of Alzheimer's disease (AD). There was also a decreased synthesis of hemoglobin mRNA, HBA and HBB, the presence of which in WBC RNA was not a result of red blood cells contamination because erythrocyte-specific marker genes were not significantly expressed. A qRT-PCR analysis of volunteer WBCs after pectin and red wine intake confirmed the complicated relationship between the plasma MeOH content and the mRNA accumulation of both genes that were previously identified, namely, GAPDH and SNX27, and genes revealed in this study, including MME, SORL1, DDIT4, HBA and HBB. We hypothesized that human plasma MeOH has an impact on the WBC mRNA levels of genes involved in cell signaling. PMID:25033451

  15. Release of formaldehyde and melamine from tableware made of melamine-formaldehyde resin.

    PubMed

    Sugita, T; Ishiwata, H; Yoshihira, K

    1990-01-01

    The relationship between the concentrations of formaldehyde and melamine released into 4% acetic acid from dishes and bowls made of melamine-formaldehyde resin was determined. The average concentrations in the migration solution after the sample had been treated at 60, 80, and 95 degrees C for 30 min with 4% acetic acid were 0.0 +/- 0.1, 0.5 +/- 0.4 and 3.0 +/- 2.2 ppm, respectively for formaldehyde and 0.04 +/- 0.07, 0.21 +/- 0.20 and 1.19 +/- 1.18 ppm, respectively for melamine. The correlation between the concentrations of formaldehyde and melamine released at 95 degrees C was y=0.4858x-0.2728 (r=0.8860), where y is melamine concentration (ppm), x is formaldehyde concentration (ppm) and r is the correlation coefficient. The molar concentration ratios of formaldehyde to melamine (F/M ratio) were 15.4 +/- 11.6 at 80 degrees C and 14.9 +/- 10.1 at 95 degrees C. Hence the release of both migrants was affected by temperature but the F/M ratio was not affected. The release of both compounds was was increased on repetition of the migration test at 95 degrees C but their concentrations remained constant after the tenth and seventeenth repetitions of the treatment. During this period, the F/M ratio decreased according to the equation 1n y=-1.4344 1n x+3.7814 (r=-0.9984) for a sample before the tenth repetition of the treatment and remained between 1.7 and 1.9 after the twelfth repetition, where y is the F/M ratio and x is the number of repetitions of the treatment.

  16. Formaldehyde and LeukemiA: Epidemiology, Potential Mechanisms and Implications for Risk Assessment

    EPA Science Inventory

    Formaldehyde is widely used in the United States and other countries. Occupational and environmental exposures to formaldehyde may be associated with an increased risk of leukemia in exposed individuals. However, risk assessment of formaldehyde and leukemia has been challenging ...

  17. Formaldehyde crosslinking: a tool for the study of chromatin complexes.

    PubMed

    Hoffman, Elizabeth A; Frey, Brian L; Smith, Lloyd M; Auble, David T

    2015-10-30

    Formaldehyde has been used for decades to probe macromolecular structure and function and to trap complexes, cells, and tissues for further analysis. Formaldehyde crosslinking is routinely employed for detection and quantification of protein-DNA interactions, interactions between chromatin proteins, and interactions between distal segments of the chromatin fiber. Despite widespread use and a rich biochemical literature, important aspects of formaldehyde behavior in cells have not been well described. Here, we highlight features of formaldehyde chemistry relevant to its use in analyses of chromatin complexes, focusing on how its properties may influence studies of chromatin structure and function.

  18. Characterization of particleboard aerosol - size distribution and formaldehyde content

    SciTech Connect

    Stumpf, J.M.; Blehm, K.D.; Buchan, R.M.; Gunter, B.J.

    1986-12-01

    Health hazards unique to particleboard include the generation of urea-formaldehyde resin bound in wood aerosol and release of formaldehyde gas that can be inhaled by the worker. A particleboard aerosol was generated by a sanding process and collected under laboratory conditions that determined the particle size distribution and formaldehyde content. Three side-by-side Marple 296 personal cascade impactors with midget impingers attached downstream collected particleboard aerosol and gaseous formaldehyde for ten sample runs. Gravimetric analysis quantified the collected aerosol mass, and chromotropic acid/spectrophotometric analytical methods were employed for formaldehyde content in particleboard aerosol and gaseous formaldehyde liberated from sanded particleboard. Significant variations (p<.005) were observed for the particleboard mass and gaseous formaldehyde collected between sample runs. No significant differences (..cap alpha.. = .05) were observed for the aerosol size distribution determined and formaldehyde content in particle board aerosol per unit mass for sampling trials. The overall MMAD of particleboard aerosol was 8.26 ..mu..mAED with a sigmag of 2.01. A predictive model was derived for determining the expected formaldehyde content (..mu..g) by particleboard aerosol mass (mg) collected and particulate size (..mu..mAED).

  19. Formaldehyde crosslinking: a tool for the study of chromatin complexes.

    PubMed

    Hoffman, Elizabeth A; Frey, Brian L; Smith, Lloyd M; Auble, David T

    2015-10-30

    Formaldehyde has been used for decades to probe macromolecular structure and function and to trap complexes, cells, and tissues for further analysis. Formaldehyde crosslinking is routinely employed for detection and quantification of protein-DNA interactions, interactions between chromatin proteins, and interactions between distal segments of the chromatin fiber. Despite widespread use and a rich biochemical literature, important aspects of formaldehyde behavior in cells have not been well described. Here, we highlight features of formaldehyde chemistry relevant to its use in analyses of chromatin complexes, focusing on how its properties may influence studies of chromatin structure and function. PMID:26354429

  20. Degradation of formaldehyde in anaerobic sequencing batch biofilm reactor (ASBBR).

    PubMed

    Pereira, N S; Zaiat, M

    2009-04-30

    The present study evaluated the degradation of formaldehyde in a bench-scale anaerobic sequencing batch reactor, which contained biomass immobilized in polyurethane foam matrices. The reactor was operated for 212 days at 35 degrees C with 8h sequential cycles, under different affluent formaldehyde concentrations ranging from 31.6 to 1104.4 mg/L (formaldehyde loading rates from 0.08 to 2.78 kg/m(3)day). The results indicate excellent reactor stability and over 99% efficiency in formaldehyde removal, with average effluent formaldehyde concentration of 3.6+/-1.7 mg/L. Formaldehyde degradation rates increased from 204.9 to 698.3mg/Lh as the initial concentration of formaldehyde was increased from around 100 to around 1100 mg/L. However, accumulation of organic matter was observed in the effluent (chemical oxygen demand (COD) values above 500 mg/L) due to the presence of non-degraded organic acids, especially acetic and propionic acids. This observation poses an important question regarding the anaerobic route of formaldehyde degradation, which might differ substantially from that reported in the literature. The anaerobic degradation pathway can be associated with the formation of long-chain oligomers from formaldehyde. Such long- or short-chain polymers are probably the precursors of organic acid formation by means of acidogenic anaerobic microorganisms. PMID:18715712

  1. Methanol crossover in direct methanol fuel cell systems.

    SciTech Connect

    Pivovar, B. S.; Bender, G.; Davey, J. R.; Zelenay, P.

    2003-01-01

    Direct methanol fuel cells (DMFCs) are currently being investigated for a number of different applications from several milliwatts to near kilowatt size scales (cell phones, laptops, auxiliary power units, etc .). Because methanol has a very high energy density, over 6000 W hr/kg, a DMFC can possibly have greatly extended lifetimes compared to the batteries, doesn't present the storage problems associated with hydrogen fuel cells and can possibly operate more efficiently and cleanly than internal combustion engines.

  2. Comparative Density Functional Study of Methanol Decomposition on Cu4 and Co4 Clusters

    SciTech Connect

    Mehmood, Faisal; Greeley, Jeffrey P.; Zapol, Peter; Curtiss, Larry A.

    2010-11-18

    A density functional theory study of the decomposition of methanol on Cu4 and Co4 clusters is presented. The reaction intermediates and activation barriers have been determined for reaction steps to form H2 and CO. For both clusters, methanol decomposition initiated by C-H and O-H bond breaking was investigated. In the case of a Cu4 cluster, methanol dehydrogenation through hydroxymethyl (CH2OH), hydroxymethylene (CHOH), formyl (CHO), and carbon monoxide (CO) is found to be slightly more favorable. For a Co4 cluster, the dehydrogenation pathway through methoxy (CH3O) and formaldehyde (CH2O) is slightly more favorable. Each of these pathways results in formation of CO and H2. The Co cluster pathway is very favorable thermodynamically and kinetically for dehydrogenation. However, since CO binds strongly, it is likely to poison methanol decomposition to H2 and CO at low temperatures. In contrast, for the Cu cluster, CO poisoning is not likely to be a problem since it does not bind strongly, but the dehydrogenation steps are not energetically favorable. Pathways involving C-O bond cleavage are even less energetically favorable. The results are compared to our previous study of methanol decomposition on Pd4 and Pd8 clusters. Finally, all reaction energy changes and transition state energies, including those for the Pd clusters, are related in a linear, Broensted-Evans-Polanyi plot.

  3. Lanthanide-Dependent Regulation of Methanol Oxidation Systems in Methylobacterium extorquens AM1 and Their Contribution to Methanol Growth

    PubMed Central

    Vu, Huong N.; Subuyuj, Gabriel A.; Vijayakumar, Srividhya; Good, Nathan M.; Martinez-Gomez, N. Cecilia

    2016-01-01

    ABSTRACT Methylobacterium extorquens AM1 has two distinct types of methanol dehydrogenase (MeDH) enzymes that catalyze the oxidation of methanol to formaldehyde. MxaFI-MeDH requires pyrroloquinoline quinone (PQQ) and Ca in its active site, while XoxF-MeDH requires PQQ and lanthanides, such as Ce and La. Using MeDH mutant strains to conduct growth analysis and MeDH activity assays, we demonstrate that M. extorquens AM1 has at least one additional lanthanide-dependent methanol oxidation system contributing to methanol growth. Additionally, the abilities of different lanthanides to support growth were tested and strongly suggest that both XoxF and the unknown methanol oxidation system are able to use La, Ce, Pr, Nd, and, to some extent, Sm. Further, growth analysis using increasing La concentrations showed that maximum growth rate and yield were achieved at and above 1 μM La, while concentrations as low as 2.5 nM allowed growth at a reduced rate. Contrary to published data, we show that addition of exogenous lanthanides results in differential expression from the xox1 and mxa promoters, upregulating genes in the xox1 operon and repressing genes in the mxa operon. Using transcriptional reporter fusions, intermediate expression from both the mxa and xox1 promoters was detected when 50 to 100 nM La was added to the growth medium, suggesting that a condition may exist under which M. extorquens AM1 is able to utilize both enzymes simultaneously. Together, these results suggest that M. extorquens AM1 actively senses and responds to lanthanide availability, preferentially utilizing the lanthanide-dependent MeDHs when possible. IMPORTANCE The biological role of lanthanides is a nascent field of study with tremendous potential to impact many areas in biology. Our studies demonstrate that there is at least one additional lanthanide-dependent methanol oxidation system, distinct from the MxaFI and XoxF MeDHs, that may aid in classifying additional environmental organisms as

  4. Oxidative decomposition of methanol on subnanometer palladium clusters : the effect of catalyst size and support composition.

    SciTech Connect

    Lee, S.; Lee, B.; Mehmood, F.; Seifert, S.; Libera, J. A.; Elam, J. W.; Greeley, J.; Zapol, P.; Curtiss, L. A.; Pellin, M. J.; Stair, P. C.; Winans, R. E; Vajda, S.; Northwestern Univ.

    2010-06-17

    Size and support effects in the oxidative decomposition of methanol on amorphous alumina supported subnanometer palladium clusters were studied under realistic reaction conditions of pressure and temperature. The smaller Pd{sub 8-12} clusters were found to promote the decomposition channel to CO and hydrogen, however with mediocre activity due to poisoning. The larger Pd{sub 15-18} clusters preferentially produce dimethyl ether and formaldehyde, without signs of posioning. A thin titania overcoat applied on the Pd{sub 15-18} improves the sintering-resistance of the catalyst. Accompanying density functional calculations confirm the posioning of small Pd clusters by CO.

  5. Oxidative Decomposition of Methanol on Subnanometer Palladium Clusters: The Effect of Catalyst Size and Support Composition

    SciTech Connect

    Lee, Sungsik; Lee, Byeongdu; Mehmood, Faisal; Seifert, Soenke; Libera, Joseph A.; Elam, J. W.; Greeley, Jeffrey P.; Zapol, Peter; Curtiss, Larry A.; Pellin, M. J.; Stair, Peter C.; Winans, R. E.; Vajda, S.

    2010-05-31

    Size and support effects in the oxidative decomposition of methanol on amorphous alumina supported subnanometer palladium clusters were studied under realistic reaction conditions of pressure and temperature. The smaller Pd8-12 clusters were found to promote the decomposition channel to CO and hydrogen, however with mediocre activity due to poisoning. The larger Pd15-18 clusters preferentially produce dimethyl ether and formaldehyde, without signs of posioning. A thin titania overcoat applied on the Pd15-18 improves the sintering-resistance of the catalyst. Accompanying density functional calculations confirm the posioning of small Pd clusters by CO.

  6. Methanol related deaths in Edirne.

    PubMed

    Azmak, Derya

    2006-01-01

    In this retrospective autopsy study, a detailed analysis of methanol related deaths in Trakya region of Turkey is presented and departmental autopsy records, toxicology and histopathology results are analyzed. We found that methanol poisonings comprise 2.83% of all forensic autopsies (n:18), 88.8% of the cases were male, most of the victims were aged between 41 and 45. Blood methanol concentrations range widely from 55 to 479 mg per 100ml. Ethyl alcohol was detected in 44.4% of the cases. Most of the cases died in hospital and were poisoned through the consumption of alcoholic beverages from illicit sources and colognes. It is important for physicians to be aware of methanol poisoning symptoms and for forensic pathologists to obtain samples for toxicology during autopsies. Some preventative strategies including to routine control of the stores, to prevent the production of illegal alcoholic beverages, etc. should be developed.

  7. Formaldehyde Absorption Toward the Gravitational Lens B0218+357 at z=0.68

    NASA Astrophysics Data System (ADS)

    Darling, J.; Wiklind, T.

    2005-12-01

    We report the detection of the ground state transition 110 - 111 of ortho-formaldehyde (H2CO) in absorption toward the Einstein ring B0218+357 at z=0.68. Combined with the 211 - 212 transition detected by Menten & Reid (1996), we obtain measurements of the excitation and column density of H2CO, estimate n(H2), and compare these to determinations made from other molecular transitions such as ammonia and CO. The excitation temperature of H2CO appears to be significantly below the local microwave background temperature, TCMB = (1+z) 2.73 K = 4.60 K, mimicking the behavior of formaldehyde in Galactic molecular clouds. We also report upper limits on the J=1/2 2Pi1/2 and J=5/2 2Pi3/2 lambda-doubled OH and CH transitions and the 51 - 60 A+ CH3OH (methanol) rotation transition toward B0218+357, B3 1504+377, and PKS 1413+135. The 110 - 111 transition of ortho-H2CO has also not been detected toward the latter two systems. Support for this work was provided by NASA through Hubble Fellowship grant HF-01183.01-A awarded by the Space Telescope Science Institute, which is operated by the Association of Universities for Research in Astronomy, Inc., for NASA, under contract NAS 5-26555.

  8. BLM protein mitigates formaldehyde-induced genomic instability

    PubMed Central

    Kumari, Anuradha; Owen, Nichole; Juarez, Eleonora; McCullough, Amanda K.

    2015-01-01

    Formaldehyde is a reactive aldehyde that has been classified as a class I human carcinogen by the International Agency for Cancer Research. There are growing concerns over the possible adverse health effects related to the occupational and environmental human exposures to formaldehyde. Although formaldehyde-induced DNA and protein adducts have been identified, the genomic instability mechanisms and the cellular tolerance pathways associated with formaldehyde exposure are not fully characterized. This study specifically examines the role of a genome stability protein, Bloom (BLM) in limiting formaldehyde-induced cellular and genetic abnormalities. Here, we show that in the absence of BLM protein, formaldehyde-treated cells exhibited increased cellular sensitivity, an immediate cell cycle arrest, and an accumulation of chromosome radial structures. In addition, live-cell imaging experiments demonstrated that formaldehyde-treated cells are dependent on BLM for timely segregation of daughter cells. Both wild-type and BLM-deficient formaldehyde-treated cells showed an accumulation of 53BP1 and γH2AX foci indicative of DNA double-strand breaks (DSBs); however, relative to wild-type cells, the BLM-deficient cells exhibited delayed repair. In response to formaldehyde exposure, we observed co-localization of 53BP1 and BLM foci at the DSB repair site, where ATM-dependent accumulation of formaldehyde-induced BLM foci occurred after the recruitment of 53BP1. Together, these findings highlight the significance of functional interactions among ATM, 53BP1, and BLM proteins as responders associated with the repair and tolerance mechanisms induced by formaldehyde. PMID:25770783

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

    SciTech Connect

    Critchley, J.A.J.H. ); Beeley, J.M.; Clark, R.J.; Buchanan, J.D. ); Summerfield, M.; Bell, S. ); Spurlock, M.S.; Edginton, J.A.G. )

    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). The 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.

  10. Formaldehyde as a trigger for protein aggregation and potential target for mitigation of age-related, progressive cognitive impairment.

    PubMed

    Su, Tao; Monte, Woodrow C; Hu, Xintian; He, Yingge; He, Rongqiao

    2016-01-01

    Recently, formaldehyde (FA), existing in a number of different cells including neural cells, was found to affect age-related cognitive impairment. Oral administration of methanol (the metabolic precursor of FA) triggers formation of senile plaques (SPs) and Tau hyperphosphorylation in the brains of monkeys with memory decline. Intraperitoneal injection of FA leads to hyperphosphorylation of Tau in wild-type mouse brains and N2a cells through activation of glycogen synthase kinase-3β (GSK-3β). Furthermore, formaldehyde at low concentrations can directly induce Tau aggregation and amyloid β (Aβ) peptide deposits in vitro. Formaldehyde-induced Tau aggregation is implicated in cytotoxicity and neural cell apoptosis. Clarifying how FA triggers Aβ deposits and Tau hyperphosphorlyation will not only improve our understanding of the molecular and cellular mechanisms of age-related cognitive impairment but will also contribute to the ongoing investigation of alternate targets for new drugs. Here, we review the role of FA, particularly that of endogenous origin, in protein aggregation and as a potential drug intervention in the development of agerelated cognitive impairment.

  11. 78 FR 51696 - Formaldehyde; Third-Party Certification Framework for the Formaldehyde Standards for Composite...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-08-21

    ... established in the Federal Register of July 23, 2013 (78 FR 44090) (FRL-9393-9). EPA is hereby extending the..., 2013, Federal Register document (78 FR 34796) (FRL-9342-4). If you have questions, consult the... Formaldehyde Standards for Composite Wood Products; Extension of Comment Period AGENCY:...

  12. 78 FR 44090 - Formaldehyde; Third-Party Certification Framework for the Formaldehyde Standards for Composite...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-07-23

    ... comment date for a proposed rule published June 10, 2013 at 78 FR 34796. Comments, identified by docket... the Federal Register of June 10, 2013 (78 FR 34796) (FRL-9342-4). EPA is hereby extending the comment... Formaldehyde Standards for Composite Wood Products; Extension of Comment Period AGENCY:...

  13. Respiratory response to formaldehyde and off-gas of urea formaldehyde foam insulation.

    PubMed Central

    Day, J H; Lees, R E; Clark, R H; Pattee, P L

    1984-01-01

    In 18 subjects, 9 of whom had previously complained of various nonrespiratory adverse effects from the urea formaldehyde foam insulation (UFFI) in their homes, pulmonary function was assessed before and after exposure in a laboratory. On separate occasions formaldehyde, 1 part per million (ppm), and UFFI off-gas yielding a formaldehyde concentration of 1.2 ppm, were delivered to each subject in an environmental chamber for 90 minutes and a fume hood for 30 minutes respectively. None of the measures of pulmonary function used (forced vital capacity, forced expiratory volume in 1 second or maximal midexpiratory flow rate) showed any clinically or statistically significant response to the exposure either immediately after or 8 hours after its beginning. There were no statistically significant differences between the responses of the group that had previously complained of adverse effects and of the group that had not. There was no evidence that either formaldehyde or UFFI off-gas operates as a lower airway allergen or important bronchospastic irritant in this heterogeneous population. Images Fig. 1 PMID:6388780

  14. Effects of endogenous formaldehyde in nasal tissues on inhaled formaldehyde dosimetry predictions in the rat, monkey, and human nasal passages.

    PubMed

    Schroeter, Jeffry D; Campbell, Jerry; Kimbell, Julia S; Conolly, Rory B; Clewell, Harvey J; Andersen, Melvin E

    2014-04-01

    Formaldehyde is a nasal carcinogen in rodents at high doses and is an endogenous compound that is present in all living cells. Due to its high solubility and reactivity, quantitative risk estimates for inhaled formaldehyde have relied on internal dose estimates in the upper respiratory tract. Dosimetry calculations are complicated by the presence of endogenous formaldehyde concentrations in the respiratory mucosa. Anatomically accurate computational fluid dynamics (CFD) models of the rat, monkey, and human nasal passages were used to simulate uptake of inhaled formaldehyde. An epithelial structure was implemented in the nasal CFD models to estimate formaldehyde absorption from air:tissue partitioning, species-specific metabolism, first-order clearance, DNA binding, and endogenous formaldehyde production. At an exposure concentration of 1 ppm, predicted formaldehyde nasal uptake was 99.4, 86.5, and 85.3% in the rat, monkey, and human, respectively. Endogenous formaldehyde in nasal tissues did not significantly affect wall mass flux or nasal uptake predictions at exposure concentrations > 500 ppb; however, reduced nasal uptake was predicted at lower exposure concentrations. At an exposure concentration of 1 ppb, predicted nasal uptake was 17.5 and 42.8% in the rat and monkey; net desorption of formaldehyde was predicted in the human model. The nonlinear behavior of formaldehyde nasal absorption will affect the dose-response analysis and subsequent risk estimates at low exposure concentrations. Updated surface area partitioning of nonsquamous epithelium and average flux values in regions where DNA-protein cross-links and cell proliferation rates were measured in rats and monkeys are reported for use in formaldehyde risk models of carcinogenesis.

  15. A ratiometric fluorescent formaldehyde probe for bioimaging applications.

    PubMed

    He, Longwei; Yang, Xueling; Liu, Yong; Kong, Xiuqi; Lin, Weiying

    2016-03-14

    We have described a ratiometric fluorescent formaldehyde probe (RFFP) based on the 6-hydroxy naphthalene chromophore for the first time. The probe is suitable for ratiometric detection of formaldehyde both in the solution and living biological samples with two distinct emission bands.

  16. Low density, resorcinol-formaldehyde aerogels

    DOEpatents

    Pekala, R.W.

    1988-05-26

    The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer ''clusters''. The covalent crosslinking of these ''clusters'' produces gels which when processed under supercritical conditions, produce low density, organic aerogels (density less than or equal to100 mg/cc; cell size less than or equal to0.1 microns). The aerogels are transparent,dark red in color and consist of interconnected colloidal-like particles with diameters of about 100 A/degree/. These aerogels may be further carbonized to form low density carbon foams with cell size of about 0.1 micron. 1 fig., 1 tab.

  17. Low density, resorcinol-formaldehyde aerogels

    DOEpatents

    Pekala, Richard W.

    1989-01-01

    The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer "clusters". The covalent crosslinking of these "clusters" produces gels which when processed under supercritical conditions, produce low density, organic aerogels (density .ltoreq.100 mg/cc; cell size .ltoreq.0.1 microns). The aerogels are transparent, dark red in color and consist of interconnected colloidal-like particles with diameters of about 100 .ANG.. These aerogels may be further carbonized to form low density carbon foams with cell size of about 0.1 micron.

  18. Low density, resorcinol-formaldehyde aerogels

    DOEpatents

    Pekala, R.W.

    1989-10-10

    The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer clusters. The covalent crosslinking of these clusters produces gels which when processed under supercritical conditions, produce low density, organic aerogels (density [<=]100 mg/cc; cell size [<=]0.1 microns). The aerogels are transparent, dark red in color and consist of interconnected colloidal-like particles with diameters of about 100 [angstrom]. These aerogels may be further carbonized to form low density carbon foams with cell size of about 0.1 micron.

  19. Low density, resorcinol-formaldehyde aerogels

    DOEpatents

    Pekala, Richard W.

    1991-01-01

    The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer "Clusters". The covalent crosslinking of these "clusters" produces gels which when processed under supercritical conditions, produce low density, organic aerogels (density.ltoreq.100 mg/cc; cell size .ltoreq.0.1 microns). The aerogels are transparent, dark red in color and consist of interconnected colloidal-like particles with diameters of about 100.circle.. These aerogels may be further carbonized to form low density carbon foams with cell size of about 0.1 micron.

  20. Importance of Diffusion in Methanol Photochemistry on TiO2(110)

    SciTech Connect

    Shen, Mingmin; Acharya, Danda P.; Dohnalek, Zdenek; Henderson, Michael A.

    2012-12-06

    The photoactivity of methanol on the rutile TiO2(110) surface is shown to depend on the ability of methanol to diffuse on the surface and find sites active for its thermal dissociation to methoxy. Temperature programmed desorption (TPD) results show that the extent of methanol photodecomposition to formaldehyde is negligible on the clean TiO2(110) surface at 100 K due to a scarcity of sites that can convert (photoinactive) methanol to (photoactive) methoxy. The extent of photoactivity at 100 K significantly increases when methanol is coadsorbed with oxygen, however only those molecules able to adsorb near (next to) a coadsorbed oxygen species are active. Preannealing coadsorbed methanol and oxygen to above 200 K prior to UV irradiation results in a significant increase in photoactivity. Scanning tunneling microscopy (STM) images clearly show that the advent of increased photoactivity in TPD correlates with the onset of methanol diffusion along the surface’s Ti4+ rows at ~200 K. These results demonstrate that optimizing thermal processes (such as diffusion or proton transfer reactions) can be critical to maximizing photocatalytic reactivity on TiO2 surfaces. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle under contract DEAC05-76RL01830. The research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.

  1. Chromogenic Detection of Aqueous Formaldehyde Using Functionalized Silica Nanoparticles.

    PubMed

    El Sayed, Sameh; Pascual, Lluı́s; Licchelli, Maurizio; Martínez-Máñez, Ramón; Gil, Salvador; Costero, Ana M; Sancenón, Félix

    2016-06-15

    Silica nanoparticles functionalized with thiol reactive units and bulky polar polyamines were used for the selective colorimetric detection of formaldehyde. The reaction of thiols groups in the nanoparticles surface with a squaraine dye resulted in loss of the π-conjugation of the chromophores, and the subsequent bleaching of the solution. However, when formaldehyde was present in the suspension, the thiol-squaraine reaction was inhibited and a chromogenic response was observed. A selective response to formaldehyde was observed only when the thiol and polyamine groups were anchored to the silica surface. The observed selective response was ascribed to the fact that bulky polyamines generate a highly polar environment around thiols, which were only able to react with the small and polar formaldehyde, but not with other aldehydes. The sensing nanoparticles showed a limit of detection (LOD) for formaldehyde of 36 ppb in water. PMID:27250594

  2. Chromogenic Detection of Aqueous Formaldehyde Using Functionalized Silica Nanoparticles.

    PubMed

    El Sayed, Sameh; Pascual, Lluı́s; Licchelli, Maurizio; Martínez-Máñez, Ramón; Gil, Salvador; Costero, Ana M; Sancenón, Félix

    2016-06-15

    Silica nanoparticles functionalized with thiol reactive units and bulky polar polyamines were used for the selective colorimetric detection of formaldehyde. The reaction of thiols groups in the nanoparticles surface with a squaraine dye resulted in loss of the π-conjugation of the chromophores, and the subsequent bleaching of the solution. However, when formaldehyde was present in the suspension, the thiol-squaraine reaction was inhibited and a chromogenic response was observed. A selective response to formaldehyde was observed only when the thiol and polyamine groups were anchored to the silica surface. The observed selective response was ascribed to the fact that bulky polyamines generate a highly polar environment around thiols, which were only able to react with the small and polar formaldehyde, but not with other aldehydes. The sensing nanoparticles showed a limit of detection (LOD) for formaldehyde of 36 ppb in water.

  3. Brain Formaldehyde is Related to Water Intake behavior

    PubMed Central

    Li, Ting; Su, Tao; He, Yingge; Lu, Jihui; Mo, Weichuan; Wei, Yan; He, Rongqiao

    2016-01-01

    A promising strategy for the prevention of Alzheimer’s disease (AD) is the identification of age-related changes that place the brain at risk for the disease. Additionally, AD is associated with chronic dehydration, and one of the significant changes that are known to result in metabolic dysfunction is an increase in the endogenous formaldehyde (FA) level. Here, we demonstrate that the levels of uric formaldehyde in AD patients were markedly increased compared with normal controls. The brain formaldehyde levels of wild-type C57 BL/6 mice increased with age, and these increases were followed by decreases in their drinking frequency and water intake. The serum arginine vasopressin (AVP) concentrations were also maintained at a high level in the 10-month-old mice. An intravenous injection of AVP into the tail induced decreases in the drinking frequency and water intake in the mice, and these decreases were associated with increases in brain formaldehyde levels. An ELISA assay revealed that the AVP injection increased both the protein level and the enzymatic activity of semicarbazide-sensitive amine oxidase (SSAO), which is an enzyme that produces formaldehyde. In contrast, the intraperitoneal injection of formaldehyde increased the serum AVP level by increasing the angiotensin II (ANG II) level, and this change was associated with a marked decrease in water intake behavior. These data suggest that the interaction between formaldehyde and AVP affects the water intake behaviors of mice. Furthermore, the highest concentration of formaldehyde in vivo was observed in the morning. Regular water intake is conducive to eliminating endogenous formaldehyde from the human body, particularly when water is consumed in the morning. Establishing good water intake habits not only effectively eliminates excess formaldehyde and other metabolic products but is also expected to yield valuable approaches to reducing the risk of AD prior to the onset of the disease. PMID:27699080

  4. Brain Formaldehyde is Related to Water Intake behavior

    PubMed Central

    Li, Ting; Su, Tao; He, Yingge; Lu, Jihui; Mo, Weichuan; Wei, Yan; He, Rongqiao

    2016-01-01

    A promising strategy for the prevention of Alzheimer’s disease (AD) is the identification of age-related changes that place the brain at risk for the disease. Additionally, AD is associated with chronic dehydration, and one of the significant changes that are known to result in metabolic dysfunction is an increase in the endogenous formaldehyde (FA) level. Here, we demonstrate that the levels of uric formaldehyde in AD patients were markedly increased compared with normal controls. The brain formaldehyde levels of wild-type C57 BL/6 mice increased with age, and these increases were followed by decreases in their drinking frequency and water intake. The serum arginine vasopressin (AVP) concentrations were also maintained at a high level in the 10-month-old mice. An intravenous injection of AVP into the tail induced decreases in the drinking frequency and water intake in the mice, and these decreases were associated with increases in brain formaldehyde levels. An ELISA assay revealed that the AVP injection increased both the protein level and the enzymatic activity of semicarbazide-sensitive amine oxidase (SSAO), which is an enzyme that produces formaldehyde. In contrast, the intraperitoneal injection of formaldehyde increased the serum AVP level by increasing the angiotensin II (ANG II) level, and this change was associated with a marked decrease in water intake behavior. These data suggest that the interaction between formaldehyde and AVP affects the water intake behaviors of mice. Furthermore, the highest concentration of formaldehyde in vivo was observed in the morning. Regular water intake is conducive to eliminating endogenous formaldehyde from the human body, particularly when water is consumed in the morning. Establishing good water intake habits not only effectively eliminates excess formaldehyde and other metabolic products but is also expected to yield valuable approaches to reducing the risk of AD prior to the onset of the disease.

  5. Partially-irreversible sorption of formaldehyde in five polymers

    NASA Astrophysics Data System (ADS)

    Ye, Wei; Cox, Steven S.; Zhao, Xiaomin; Frazier, Charles E.; Little, John C.

    2014-12-01

    Due to its environmental ubiquity and concern over its potential toxicity, the mass-transfer characteristics of formaldehyde are of critical importance to indoor air quality research. Previous studies have suggested that formaldehyde mass transfer in polymer is partially irreversible. In this study, mechanisms that could cause the observed irreversibility were investigated. Polycarbonate and four other polymeric matrices were selected and subjected to formaldehyde sorption/desorption cycles. Mass transfer of formaldehyde was partially irreversible in all cases, and three potential mechanisms were evaluated. First, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) analysis was used to investigate possible formaldehyde polymerization on polymer surfaces. ATR-FTIR showed no detectable paraformaldehyde or formaldehyde on the film surfaces that had been exposed to formaldehyde and air. ATR-FTIR did detect aliphatic acids suggesting oxidation had occurred on film surfaces as a result of exposure to formaldehyde. However, additional study suggested that air is not the primary cause for irreversibility. Second, statistical physics theory was tested as a possible explanation. According to this theory, reversible and irreversible sorption could be taking place simultaneously. The irreversible fraction should be constant during sorption and the fraction could be determined by performing a complete sorption/desorption test. The sorption/desorption data was consistent with this theory. Third, chemisorption was considered as another possible cause for irreversibility. Extraction/fluorimetry testing of post-sorption and post-desorption polymer films showed measurable quantities of formaldehyde suggesting that some of the chemisorbed formaldehyde was reversible at the higher extraction temperature. Further quantitative study on chemical reaction products is needed.

  6. Gas-phase reactivity of metavanadate [VO3]- towards methanol and ethanol: experiment and theory.

    PubMed

    Waters, Tom; Wedd, Anthony G; O'Hair, Richard A J

    2007-01-01

    The gas-phase reactivity of the metavanadate anion [VO3]- towards methanol and ethanol was examined by a combination of ion-molecule reaction and isotope labelling experiments in a quadrupole ion-trap mass spectrometer. The experimental data were interpreted with the aid of density functional theory calculations. [VO3]- dehydrated methanol to eliminate water and form [VO2(eta2-OCH2)]-, which features an [eta2-C,O-OCH2]2- ligand formed by formal removal of two protons from methanol and which is isoelectronic with peroxide. [VO3]- reacted with ethanol in an analogous manner to form [VO2(eta2-OCHCH3)]-, as well as by loss of ethene to form [VO2(OH)2]-. The calculations predicted that important intermediates in these reactions were the hydroxo alkoxo anions [VO2(OH)(OCH2R)]- (R: H, CH3). These were predicted to undergo intramolecular hydrogen-atom transfer to form [VO(OH)2(eta1-OCHR)]- followed by eta1-O-->eta2-C,O rearrangements to form [VO(OH)2(eta2-OCHR)]-. The latter reacted further to eliminate water and generate the product [VO2(eta2-OCHR)]-. This major product observed for [VO3]- is markedly different from that observed previously for [NbO3]- containing the heavier Group 5 congener niobium. In that case, the major product of the reaction was an ion of stoichiometry [Nb, O3, H2]- arising from the formal dehydrogenation of methanol to formaldehyde. The origin of this difference was examined theoretically and attributed to the intermediate alkoxo anion [NbO2(OH)(OCH3)]- preferring hydride transfer to form [HNbO2(OH)]- with loss of formaldehyde. This contrasts with the hydrogen-atom-transfer pathway observed for [VO2(OH)(OCH3)]-. PMID:17661322

  7. Passive emission colorimetric sensor (PECS) for measuring emission rates of formaldehyde based on an enzymatic reaction and reflectance photometry.

    PubMed

    Shinohara, Naohide; Kajiwara, Tomohisa; Ohnishi, Masato; Kodama, Kenichi; Yanagisawa, Yukio

    2008-06-15

    A coin-sized passive emission colorimetric sensor (PECS) based on an enzymatic reaction and a portable reflectance photometry device were developed to determine the emission rates of formaldehyde from building materials and other materials found indoors in only 30 minutes on-site. The color change of the PECS linearly correlated to the concentration of formaldehyde aqueous solutions up to 28 microg/mL. The correlation between the emission rates measured by using the PECS and those measured by using a desiccator method or by using a chamber method was fitted with a linear function and a power function, and the determination coefficients were more than 0.98. The reproducible results indicate that the emission rates could be obtained with the correlation equations from the data measured by using the PECS and the portable reflectance photometry device. Limits of detection (LODs) were 0.051 mg/L for the desiccator method and 3.1 microg/m2/h for the chamber method. Thus, it was confirmed that the emission rates of formaldehyde from the building materials classified as F four-star (< 0.3 mg/L (desiccator method) or < 5.0 microg/m2/h (chamber method)), based on Japanese Industrial Standards (JIS), could be measured with the PECS. The measurement with PECS was confirmed to be precise (RSD < 10%). Other chemicals emitted from indoor materials, such as methanol, ethanol, acetone, toluene, and xylene, interfered little with the measurement of formaldehyde emission rates by using the PECS.

  8. Formaldehyde exposure and acute health effects study

    SciTech Connect

    Quackenboss, J.J.; Lebowitz, M.D.; Michaud, J.P.; Bronnimann, D. )

    1989-01-01

    To assess the effects of formaldehyde exposures on health, exposure groups were defined using baseline exposure and health questionnaires. Formaldehyde concentrations were poorly correlated with these exposure classifications, perhaps due to the time delay between classification and monitoring. The 151 households reported here had a mean HCHO concentration of 35 (S.E. 1.5 and median 30) {mu}g/m{sup 3}. Passive samplers prepared in our lab were calibrated in a chamber to derive an estimated sampling rate of 0.311 {mu}g/(mg {center dot} m{sup {minus}3} {center dot} hr). They were also compared to commercially available samplers inside of the homes, with a correlation coefficient of 0.896 and mean difference of 2.6 {mu}g/m{sup 3}. In this report of initial findings from an ongoing study, daily symptoms and peak expiratory flow measurements were compared with an HCHO exposure classification based on the median measured concentrations. None of the symptoms groups were related to HCHO exposure when controlling for age and sex. There was a significant relationship between HCHO exposure and variability in peak expiratory flows that was dependent on age group. It may be especially important to assess the variability in reactive individuals and children to determine the short-term effects of HCHO exposures and possible long-term consequences.

  9. Mechanical properties of melamine-formaldehyde microcapsules.

    PubMed

    Sun, G; Zhang, Z

    2001-01-01

    The mechanical properties of melamine-formaldehyde (M-F) microcapsules were studied using a micromanipulation technique. Single microcapsules with diameters of 1-12 microm were compressed and held between two parallel planes, compressed and released, and compressed to burst at different speeds, whilst the force being imposed on the microcapsules and their deformation were measured simultaneously. This force increased as single microcapsules were compressed and then relaxed slightly as they were held. When the microcapsules were repeatedly compressed and released, a pseudo yield point was found for each microcapsule. Before the microcapsules were compressed to this point, the deformed microcapsules recovered to their original shape once the force was removed. However, when the deformation was beyond the 'yield point' there was profound hysteresis and the microcapsules showed plastic behaviour. As the microcapsules were compressed to burst at different speeds, ranging from 0.5-6.0 microm/s, it was found that their mean bursting forces did not change significantly. The deformations at the pseudo yield point and at bursting were also independent of the compression speed. On average, these melamine-formaldehyde microcapsules reached their 'yield point' at a deformation of about 19 +/- 1%, and burst at a deformation of 70 +/- 1%.

  10. ACTION OF FORMALDEHYDE ON ENZYMES AND ON CERTAIN PBOTEIDS

    PubMed Central

    Bliss, C. L.; Novy, F. G.

    1899-01-01

    The following general conclusions may be drawn from the preceding work: Fibrin is altered by formaldehyde and is then less easily digested by pepsin and by trypsin. Papaïn is apparently unable to digest fibrin even when this is exposed to very weak formaldehyde (1:1000) for a very short time. The casein of milk, on contact with formaldehyde, undergoes rapid alteration and is as a result not coagulated by rennet, or but very slowly. Such altered casein, like similar fibrin, is not readily digested by the proteolytic ferments. The longer the formaldehyde acts on casein and on fibrin the more marked is the result. Pepsin is not affected by a one per cent solution of formaldehyde, even when the mixture has stood for four weeks. Even a five per cent solution of formaldehyde acting for three weeks has no effect on pepsin. Contrary results obtained by others are due to an alteration of the fibrin by the formaldehyde. A putrid solution of pepsin in distilled water one month old digests fibrin as readily as a fresh solution. Rennet is not affected even by a four per cent solution of formaldehyde acting for several weeks. The absence of coagulation at times is due to the action of formaldehyde on the casein of the milk and not on the rennet ferment. Papaïn is very quickly altered by formaldehyde, even in very dilute solution. Moreover, it is unable to digest fibrin that has been exposed to the action of a very dilute solution of formaldehyde for a short time. Trypsin is altered by formaldehyde to such an extent that digestion of fibrin will not take place, or but very slowly. The extent to which trypsin is affected by formaldehyde depends largely upon the amount of organic matter present, as well as on the amount of ferment in the solution. Amylopsin is not destroyed by very dilute solutions of formaldehyde, but stronger solutions decrease the activity of the ferment, and if used in sufficient concentration will destroy it completely. Ptyalin, like the diastatic ferment of

  11. Rapid starting methanol reactor system

    DOEpatents

    Chludzinski, Paul J.; Dantowitz, Philip; McElroy, James F.

    1984-01-01

    The invention relates to a methanol-to-hydrogen cracking reactor for use with a fuel cell vehicular power plant. The system is particularly designed for rapid start-up of the catalytic methanol cracking reactor after an extended shut-down period, i.e., after the vehicular fuel cell power plant has been inoperative overnight. Rapid system start-up is accomplished by a combination of direct and indirect heating of the cracking catalyst. Initially, liquid methanol is burned with a stoichiometric or slightly lean air mixture in the combustion chamber of the reactor assembly. The hot combustion gas travels down a flue gas chamber in heat exchange relationship with the catalytic cracking chamber transferring heat across the catalyst chamber wall to heat the catalyst indirectly. The combustion gas is then diverted back through the catalyst bed to heat the catalyst pellets directly. When the cracking reactor temperature reaches operating temperature, methanol combustion is stopped and a hot gas valve is switched to route the flue gas overboard, with methanol being fed directly to the catalytic cracking reactor. Thereafter, the burner operates on excess hydrogen from the fuel cells.

  12. Selective methanol or formate production during continuous CO₂ fermentation by the acetogen biocatalysts engineered via integration of synthetic pathways using Tn7-tool.

    PubMed

    Tyurin, Michael; Kiriukhin, Michael

    2013-09-01

    Methanol-resistant mutant acetogen Clostridium sp. MT1424 originally producing only 365 mM acetate from CO₂/CO was engineered to eliminate acetate production and spore formation using Cre-lox66/lox71-system to power subsequent methanol production via expressing synthetic methanol dehydrogenase, formaldehyde dehydrogenase and formate dehydrogenase, three copies of each, assembled in cluster and integrated to chromosome using Tn7-based approach. Production of 2.2 M methanol was steady (p < 0.005) in single step fermentations of 20 % CO₂ + 80 % H₂ blend (v/v) 25 day runs each in five independent repeats. If the integrated cluster comprised only three copies of formate dehydrogenase the respective recombinants produced 95 mM formate (p < 0.005) under the same conditions. For commercialization, the suggested source of inorganic carbon would be CO₂ waste of IGCC power plant. Hydrogen may be produced in situ via powered by solar panels electrolysis.

  13. Selective methanol or formate production during continuous CO₂ fermentation by the acetogen biocatalysts engineered via integration of synthetic pathways using Tn7-tool.

    PubMed

    Tyurin, Michael; Kiriukhin, Michael

    2013-09-01

    Methanol-resistant mutant acetogen Clostridium sp. MT1424 originally producing only 365 mM acetate from CO₂/CO was engineered to eliminate acetate production and spore formation using Cre-lox66/lox71-system to power subsequent methanol production via expressing synthetic methanol dehydrogenase, formaldehyde dehydrogenase and formate dehydrogenase, three copies of each, assembled in cluster and integrated to chromosome using Tn7-based approach. Production of 2.2 M methanol was steady (p < 0.005) in single step fermentations of 20 % CO₂ + 80 % H₂ blend (v/v) 25 day runs each in five independent repeats. If the integrated cluster comprised only three copies of formate dehydrogenase the respective recombinants produced 95 mM formate (p < 0.005) under the same conditions. For commercialization, the suggested source of inorganic carbon would be CO₂ waste of IGCC power plant. Hydrogen may be produced in situ via powered by solar panels electrolysis. PMID:23519429

  14. Identification of active sites in gold-catalyzed hydrogenation of acrolein.

    PubMed

    Mohr, Christian; Hofmeister, Herbert; Radnik, Jörg; Claus, Peter

    2003-02-19

    The active sites of supported gold catalysts, favoring the adsorption of C=O groups of acrolein and subsequent reaction to allyl alcohol, have been identified as edges of gold nanoparticles. After our recent finding that this reaction preferentially occurs on single crystalline particles rather than multiply twinned ones, this paper reports on a new approach to distinguish different features of the gold particle morphology. Elucidation of the active site issue cannot be simply done by varying the size of gold particles, since the effects of faceting and multiply twinned particles may interfere. Therefore, modification of the gold particle surface by indium has been used to vary the active site characteristics of a suitable catalyst, and a selective decoration of gold particle faces has been observed, leaving edges free. This is in contradiction to theoretical predictions, suggesting a preferred occupation of the low-coordinated edges of the gold particles. On the bimetallic catalyst, the desired allyl alcohol is the main product (selectivity 63%; temperature 593 K, total pressure p(total) = 2 MPa). From the experimentally proven correlation between surface structure and catalytic behavior, the edges of single crystalline gold particles have been identified as active sites for the preferred C=O hydrogenation. PMID:12580618

  15. Emissions of acrolein and other aldehydes from biodiesel-fueled heavy-duty vehicles.

    PubMed

    Cahill, Thomas M; Okamoto, Robert A

    2012-08-01

    Aldehyde emissions were measured from two heavy-duty trucks, namely 2000 and 2008 model year vehicles meeting different EPA emission standards. The tests were conducted on a chassis dynamometer and emissions were collected from a constant volume dilution tunnel. For the 2000 model year vehicle, four different fuels were tested, namely California ultralow sulfur diesel (CARB ULSD), soy biodiesel, animal biodiesel, and renewable diesel. All of the fuels were tested with simulated city and high speed cruise drive cycles. For the 2008 vehicle, only soy biodiesel and CARB ULSD fuels were tested. The research objective was to compare aldehyde emission rates between (1) the test fuels, (2) the drive cycles, and (3) the engine technologies. The results showed that soy biodiesel had the highest acrolein emission rates while the renewable diesel showed the lowest. The drive cycle also affected emission rates with the cruise drive cycle having lower emissions than the urban drive cycle. Lastly, the newer vehicle with the diesel particulate filter had greatly reduced carbonyl emissions compared to the other vehicles, thus demonstrating that the engine technology had a greater influence on emission rates than the fuels. PMID:22746209

  16. Vibrationally specific photoionization cross sections of acrolein leading to the X̃²A' ionic state.

    PubMed

    López-Domínguez, Jesús A; Lucchese, Robert R; Fulfer, K D; Hardy, David; Poliakoff, E D; Aguilar, A A

    2014-09-01

    The vibrational branching ratios in the photoionization of acrolein for ionization leading to the X̃²A' ion state were studied. Computed logarithmic derivatives of the cross section and the corresponding experimental data derived from measured vibrational branching ratios for several normal modes (ν9, ν10, ν11, and ν12) were found to be in relatively good agreement, particularly for the lower half of the 11-100 eV photon energy range considered. Two shape resonances have been found near photon energies of 15.5 and 23 eV in the photoionization cross section and have been demonstrated to originate from the partial cross section of the A' scattering symmetry. The wave functions computed at the resonance complex energies are delocalized over the whole molecule. By looking at the dependence of the cross section on the different normal mode displacements together with the wave function at the resonant energy, a qualitative explanation is given for the change of the cross sections with respect to changing geometry.

  17. Cigarette Smoke Component Acrolein Modulates Chromatin Assembly by Inhibiting Histone Acetylation*

    PubMed Central

    Chen, Danqi; Fang, Lei; Li, Hongjie; Tang, Moon-shong; Jin, Chunyuan

    2013-01-01

    Chromatin structure and gene expression are both regulated by nucleosome assembly. How environmental factors influence histone nuclear import and the nucleosome assembly pathway, leading to changes in chromatin organization and transcription, remains unknown. Acrolein (Acr) is an α,β-unsaturated aldehyde, which is abundant in the environment, especially in cigarette smoke. It has recently been implicated as a potential major carcinogen of smoking-related lung cancer. Here we show that Acr forms adducts with histone proteins in vitro and in vivo and preferentially reacts with free histones rather than with nucleosomal histones. Cellular fractionation analyses reveal that Acr exposure specifically inhibits acetylations of N-terminal tails of cytosolic histones H3 and H4, modifications that are important for nuclear import and chromatin assembly. Notably, Acr exposure compromises the delivery of histone H3 into chromatin and increases chromatin accessibility. Moreover, changes in nucleosome occupancy at several genomic loci are correlated with transcriptional responses to Acr exposure. Our data provide new insights into mechanisms whereby environmental factors interact with the genome and influence genome function. PMID:23770671

  18. Effects of acetaldehyde and acrolein on blood pressure in guanethidine-pretreated hypertensive rats

    SciTech Connect

    Green, M.A.; Egle, J.L. Jr.

    1983-06-15

    These experiments were undertaken to study the effect of the interaction of the antihypertensive agent guanethidine and two aldehydes possessing sympathomimetic activity on the blood pressure of spontaneously hypertensive rats (SHR). Acetaldehyde, when administered iv to acutely guanethidine-pretreated (15 mg/kg) SHRs under urethane anesthesia, caused a potentiated pressor response in the dose range of 3 to 40 mg/kg. When administered iv to chronically guanethidine-pretreated SHRs, a pressor response was noted at low doses and a depressor response at high doses. Acrolein (0.05 to 0.5 mg/kg) produced a pressor response at low doses and a depressor response at high doses in both acutely and chronically guanethidine-pretreated SHRs. Pressor responses, particularly to acetaldehyde, may be due to an enlarged tyramine-releasable pool, hyperreactivity of alpha adrenergic receptors of SHRs, or guanethidine inhibition of norepinephrine reuptake. Depressor responses to high doses of aldehydes may be attributed to vagal stimulation or direct vasodilation. It is concluded that there is a significant interaction between the aldehydes and guanethidine which may have implications for someone undergoing treatment with guanethidine for hypertension while being exposed to acetaldehyde and related compounds from ethanol and tobacco smoke.

  19. Cigarette smoke component acrolein modulates chromatin assembly by inhibiting histone acetylation.

    PubMed

    Chen, Danqi; Fang, Lei; Li, Hongjie; Tang, Moon-shong; Jin, Chunyuan

    2013-07-26

    Chromatin structure and gene expression are both regulated by nucleosome assembly. How environmental factors influence histone nuclear import and the nucleosome assembly pathway, leading to changes in chromatin organization and transcription, remains unknown. Acrolein (Acr) is an α,β-unsaturated aldehyde, which is abundant in the environment, especially in cigarette smoke. It has recently been implicated as a potential major carcinogen of smoking-related lung cancer. Here we show that Acr forms adducts with histone proteins in vitro and in vivo and preferentially reacts with free histones rather than with nucleosomal histones. Cellular fractionation analyses reveal that Acr exposure specifically inhibits acetylations of N-terminal tails of cytosolic histones H3 and H4, modifications that are important for nuclear import and chromatin assembly. Notably, Acr exposure compromises the delivery of histone H3 into chromatin and increases chromatin accessibility. Moreover, changes in nucleosome occupancy at several genomic loci are correlated with transcriptional responses to Acr exposure. Our data provide new insights into mechanisms whereby environmental factors interact with the genome and influence genome function.

  20. The mechanism of the oxidation of propene to acrolein over antimony - Tin mixed oxide catalysts

    SciTech Connect

    Ono, Takehiko ); Hillig, K.W. II; Kuczkowski, R.L. )

    1990-05-01

    The oxidation of propenes such as {sup 13}CH{sub 2}{double bond}CH-CH{sub 3}, CH{sub 2}{double bond}CH-CD{sub 3}, cis-CHD{double bond}CD-CH{sub 3}, and CH{sub 2}{double bond}CH-CH{sub 3} was studied over Sb{sub 6}O{sub 13}, SnO{sub 2}, and Sb-Sn mixed oxide catalysts. The results with {sup 13}CH{sub 2}{double bond}CH-CH{sub 3} and CH{sub 2}{double bond}CH-CD{sub 3} were consistent with a {pi}-allyl intermediate. The isotope effect for allylic hydrogen abstraction was 1/0.55 (k{sub H}/k{sub D}) over the Sb-Sn oxide catalysts, indicating that this is the slowest step in the formation of acrolein as with other catalyst systems. The oxidation of CHD{double bond}CH-CH{sub 3} did not exhibit a marked isotope effect for the second hydrogen abstraction. This is inconsistent with a fast {pi}-allyl to {sigma}-allyl equilibration process or the irreversible {pi}-allyl to {sigma}-allyl conversion observed over other metal oxide catalysts. The absence of an isotope effect is similar to oxidations over rhodium. The roles of Sn and Sb ions in the oxidation are also discussed.

  1. Emissions of acrolein and other aldehydes from biodiesel-fueled heavy-duty vehicles.

    PubMed

    Cahill, Thomas M; Okamoto, Robert A

    2012-08-01

    Aldehyde emissions were measured from two heavy-duty trucks, namely 2000 and 2008 model year vehicles meeting different EPA emission standards. The tests were conducted on a chassis dynamometer and emissions were collected from a constant volume dilution tunnel. For the 2000 model year vehicle, four different fuels were tested, namely California ultralow sulfur diesel (CARB ULSD), soy biodiesel, animal biodiesel, and renewable diesel. All of the fuels were tested with simulated city and high speed cruise drive cycles. For the 2008 vehicle, only soy biodiesel and CARB ULSD fuels were tested. The research objective was to compare aldehyde emission rates between (1) the test fuels, (2) the drive cycles, and (3) the engine technologies. The results showed that soy biodiesel had the highest acrolein emission rates while the renewable diesel showed the lowest. The drive cycle also affected emission rates with the cruise drive cycle having lower emissions than the urban drive cycle. Lastly, the newer vehicle with the diesel particulate filter had greatly reduced carbonyl emissions compared to the other vehicles, thus demonstrating that the engine technology had a greater influence on emission rates than the fuels.

  2. 21 CFR 177.1900 - Urea-formaldehyde resins in molded articles.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Urea-formaldehyde resins in molded articles. 177...-formaldehyde resins in molded articles. Urea-formaldehyde resins may be safely used as the food-contact surface... conditions: (a) For the purpose of this section, urea-formaldehyde resins are those produced when 1 mole...

  3. 21 CFR 177.1460 - Melamine-formaldehyde resins in molded articles.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Melamine-formaldehyde resins in molded articles...-formaldehyde resins in molded articles. Melamine-formaldehyde resins may be safely used as the food-contact...: (a) For the purpose of this section, melamine-formaldehyde resins are those produced when 1 mole...

  4. 21 CFR 177.1460 - Melamine-formaldehyde resins in molded articles.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Melamine-formaldehyde resins in molded articles...-formaldehyde resins in molded articles. Melamine-formaldehyde resins may be safely used as the food-contact...: (a) For the purpose of this section, melamine-formaldehyde resins are those produced when 1 mole...

  5. 21 CFR 177.1460 - Melamine-formaldehyde resins in molded articles.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Melamine-formaldehyde resins in molded articles...-formaldehyde resins in molded articles. Melamine-formaldehyde resins may be safely used as the food-contact...: (a) For the purpose of this section, melamine-formaldehyde resins are those produced when 1 mole...

  6. 21 CFR 177.1460 - Melamine-formaldehyde resins in molded articles.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Melamine-formaldehyde resins in molded articles...-formaldehyde resins in molded articles. Melamine-formaldehyde resins may be safely used as the food-contact...: (a) For the purpose of this section, melamine-formaldehyde resins are those produced when 1 mole...

  7. Proportional mortality patterns among chemical plant workers exposed to formaldehyde.

    PubMed Central

    Marsh, G M

    1982-01-01

    To examine the possible health risks associated with occupational exposure to formaldehyde a proportional mortality analysis was conducted on deaths occurring between 1950 and 1976 among 136 men who had been employed a month or more in one of five formaldehyde-related areas of a large chemical producing plant located in Springfield, Massachusetts, USA. Overall, no statistically significant excesses or deficits in proportional mortality were observed among the formaldehyde-exposed group based on comparisons with both United States men and men from the local county area. In addition, no important differences in mortality were observed among this group when comparisons were made with 456 male decedents from the same plant who had not had a month or more of formaldehyde exposure. Within the calendar period examined, no deaths from sinonasal cancer were observed among the chemical workers studied nor was mention made on any death certificate of sinonasal cancer as a contributory cause of death. No important excesses, trends, or patterns in cancer mortality were observed among white male formadelhyde-exposed workers when consideration was given to age and time period of death, type and duration of formaldehyde exposure, and the lapse period from the onset of the first formaldehyde-related job assignment. Although certain limitations of this study do not allow definite conclusions to be drawn, the results indicate no trends or patterns in proportional mortality that could be directly linked to exposures to formaldehyde. PMID:7138792

  8. Determination of trace amounts of formaldehyde in acetone.

    PubMed

    Huang, X H Hilda; Ip, H S Simon; Yu, Jian Zhen

    2007-12-01

    A method to quantify sub-ppm levels of formaldehyde in acetone has been developed and it is reported here. In this method, the different reactivities and stabilities of sulfite with formaldehyde and acetone are used to separate the two carbonyl compounds. Sulfite reacts with formaldehyde to form hydroxymethanesulfonate (HMS), the non-volatile and stable nature of which allows its separation from bulk acetone solvent. The resulting HMS is then converted back to formaldehyde under basic conditions, and formaldehyde is derivatized with 2,4-dinitrophenylhydrazine (DNPH) and quantified in its DNP hydrazone form using high-performance liquid chromatography-UV detection. The method detection limit at the 99% confidence level was 0.051 mg L(-1). A batch of samples can be processed within 4 h. The method has been applied to quantify the amount of formaldehyde in an analytical-grade acetone and in a commercial nail polish remover and the level of formaldehyde was found to be 0.175 and 0.184 mg L(-1), respectively. PMID:17996534

  9. A survey of formaldehyde in shampoos and skin creams on the Danish market.

    PubMed

    Rastogi, S C

    1992-10-01

    To evaluate the exposure of the general population to formaldehyde from the use of cosmetic products, as well as to monitor whether cosmetic products comply with national regulations, 285 shampoos, creams, etc., were analysed for formaldehyde. Identification and determination of formaldehyde was performed by the EEC method for the analysis of formaldehyde in cosmetic products. It was shown that 29.5% of the products investigated contained 0.001%-0.147% total formaldehyde. In 10 of the products (3.5%), total formaldehyde content was > 0.05%. 8 of these products contained > 0.05% free formaldehyde. None of these products was labelled 'contains formaldehyde'. 17 of the products investigated were declared to contain specific formaldehyde-releasers. Formaldehyde could not be detected (detection limit 0.001%) in cosmetic products that were declared to contain Bronidox/Bronopol.

  10. Dehydrogenation of anhydrous methanol at room temperature by o-aminophenol-based photocatalysts.

    PubMed

    Wakizaka, Masanori; Matsumoto, Takeshi; Tanaka, Ryota; Chang, Ho-Chol

    2016-01-01

    Dehydrogenation of anhydrous methanol is of great importance, given its ubiquity as an intermediate for the production of a large number of industrial chemicals. Since dehydrogenation of methanol is an endothermic reaction, heterogeneous or homogeneous precious-metal-based catalysts and high temperatures are usually required for this reaction to proceed. Here we report the photochemical dehydrogenation of anhydrous methanol at room temperature catalysed by o-aminophenol (apH2), o-aminophenolate (apH(-)) and the non-precious metal complex trans-[Fe(II)(apH)2(MeOH)2]. Under excitation at 289±10 nm and in the absence of additional photosensitizers, these photocatalysts generate hydrogen and formaldehyde from anhydrous methanol with external quantum yields of 2.9±0.15%, 3.7±0.19% and 4.8±0.24%, respectively, which are the highest values reported so far to the best of our knowledge. Mechanistic investigations reveal that the photo-induced formation of hydrogen radicals triggers the reaction. PMID:27457731

  11. Dehydrogenation of anhydrous methanol at room temperature by o-aminophenol-based photocatalysts

    PubMed Central

    Wakizaka, Masanori; Matsumoto, Takeshi; Tanaka, Ryota; Chang, Ho-Chol

    2016-01-01

    Dehydrogenation of anhydrous methanol is of great importance, given its ubiquity as an intermediate for the production of a large number of industrial chemicals. Since dehydrogenation of methanol is an endothermic reaction, heterogeneous or homogeneous precious-metal-based catalysts and high temperatures are usually required for this reaction to proceed. Here we report the photochemical dehydrogenation of anhydrous methanol at room temperature catalysed by o-aminophenol (apH2), o-aminophenolate (apH−) and the non-precious metal complex trans-[FeII(apH)2(MeOH)2]. Under excitation at 289±10 nm and in the absence of additional photosensitizers, these photocatalysts generate hydrogen and formaldehyde from anhydrous methanol with external quantum yields of 2.9±0.15%, 3.7±0.19% and 4.8±0.24%, respectively, which are the highest values reported so far to the best of our knowledge. Mechanistic investigations reveal that the photo-induced formation of hydrogen radicals triggers the reaction. PMID:27457731

  12. Online Monitoring of Methanol Electro-Oxidation Reactions by Ambient Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Cheng, Si; Wu, Qiuhua; Dewald, Howard D.; Chen, Hao

    2016-08-01

    Online detection of methanol electro-oxidation reaction products [e.g., formaldehyde (HCHO)] by mass spectrometry (MS) is challenging, owing to the high salt content and extreme pH of the electrolyte solution as well as the difficulty in ionizing the reaction products. Herein we present an online ambient mass spectrometric approach for analyzing HCHO generated from methanol electro-oxidation, taking the advantage of high salt tolerance of desorption electrospray ionization mass spectrometry (DESI-MS). It was found that HCHO can be detected as PhNHNH+=CH2 (m/z 121) by DESI after online derivatization with PhNHNH2. With this approach, the analysis of HCHO from methanol electro-oxidation by MS was carried out not only in acidic condition but also in alkaline media for the first time. Efficiencies of different electrodes for methanol oxidation at different pHs were also evaluated. Our results show that Au electrode produces more HCHO than Pt-based electrodes at alkaline pH, while the latter have higher yields at acidic solution. The presented methodology would be of great value for elucidating fuel cell reaction mechanisms and for screening ideal fuel cell electrode materials.

  13. INSTRUCTIONS FOR OPERATING LBL FORMALDEHYDE SAMPLER

    SciTech Connect

    Fanning, L.Z.; Allen, J.R.; Miksch, R.R.

    1981-09-01

    The LBL formaldehyde sampler consists of two parts: 1) a pump box and 2) a small refrigerator housing sampling bubblers. The pump box contains two pumps, a timer, a flow controller, an electrical cord, and a ten-foot piece of tubing to connect the refrigerator to the pump box. The small refrigerator contains four columns of bubbler sampling trains attached to a metal plate. Two sampling trains each are plumbed in parallel to two sampling ports on the back of the refrigerator. The two sampling lines supplied are to be attached to these ports to allow two locations to be sampled at once (usually one indoor and one outdoor). The refrigerator also contains a rack for holding bubbler tubes. In the sampling process, air is drawn through a sampling line attached to the fitting at the back of the refrigerator and into a prlmary bubbler containing a trapping solution. This trapping solution can be distilled water or an aqueous solution of some compound that reacts with formaldehyde. From this bubbler the air goes through a second bubbler containing the same trapping solution as the first bubbler. (To maintain sample integrity, all parts that the air sample contacts are made of Teflon, polypropylene, and stainless steel.) The air then goes into the third bubbler, which contains no liquid. This bubbler contains a hypodermic needle that serves as a flow-control orifice. The hypodermic needle, in conjunction with the flow controller in the pump box, ensures a constant a flow rate. The refrigerator contains four columns of these sets of three bubblers. After samples have been collected, the bubbler bottoms are detached and the contents of the first and second bubblers in each column are poured together, capped, and labeled. The use of a refrigerated primary and secondary bubbler whose contents are combined at the end of a sampling period ensures 95% collection efficiency. After the bubbler tubes are capped and labeled, they are stored either in the rack supplied in the

  14. Synthesis and properties of melamine-formaldehyde/ montmorillonite nanocomposites.

    PubMed

    Wang, Haitao; Meng, Xiangfu; Qian, Zhongzhong; Zhoul, Hu; Ding, Yanfen; Zhang, Shimin; Yang, Mingshu

    2008-04-01

    In this paper, intercalated and partially exfoliated melamine-formaldehyde (MF)/montmorillonite (MMT) nanocomposites have been synthesized successfully via in-situ polymerization based on pristine montmorillonite, acidified montmorillonite and organic modified montmorillonite respectively. The obtained nanocomposites were characterized by XRD, TEM, TGA, and Raman spectroscopy. Free formaldehyde content of those composites was also determined by acetyl acetone technique. It was found that acidified montmorillonite and organic modified montmorillonite could catalyze the polycondensation reaction of methylolmelamines. The thermal stability and chemical resistance of those two nanocomposites were also improved dramatically compared to pure melamine-formaldehyde resin.

  15. Formaldehyde: a candidate toxic air contaminant. Final report

    SciTech Connect

    Frye, B.; Parker, T.

    1988-03-01

    Formaldehyde (HCHO) is a gas widely used in adhesives and resins, textiles, embalming fluids, fungicides, air fresheners, and cosmetics. It is directly emitted into the ambient outdoor air from vehicular and stationary sources, and is also produced in the atmosphere from other substances by photochemical smog processes. The International Agency for Research on Cancer (IARC) has determined that there is sufficient evidence for carcinogenicity of formaldehyde to animals, and limited evidence for carcinogenicity to humans. EPA classifies formaldehyde as a probable human carcinogen with a one in a million risk concentration of 0.08 ppb.

  16. Evolution of active catalysts for the selective oxidative dehydrogenation of methanol on Fe2O3 surface doped with Mo oxide.

    PubMed

    Bowker, M; Brookes, C; Carley, A F; House, M P; Kosif, M; Sankar, G; Wawata, I; Wells, P P; Yaseneva, P

    2013-08-01

    Iron molybdate catalysts are used for the selective oxidation of methanol to formaldehyde. In this paper we have attempted to understand what determines high selectivity in this reaction system by doping haematite with surface layers of Mo by incipient wetness impregnation. This works well and the Mo appears to form finely dispersed layers. Even very low loadings of Mo have a marked effect on improving the selectivity to formaldehyde. Haematite itself is a very poor catalyst with high selectivity to combustion products, whereas, when only 0.25 monolayers of Mo are deposited on the surface, formaldehyde and CO selectivities are greatly enhanced and CO2 production is greatly diminished. However, even with as much as seven monolayers of Mo dosed on to the surface, these materials achieve much less selectivity to formaldehyde at high conversion than do the industrial catalysts. The reason for this is that the Mo forms a 'skin' of ferric molybdate on a core of iron oxide, but does not produce a pure Mo oxide monolayer on the surface, a situation which is essential for very high yields of formaldehyde. PMID:23552323

  17. A SUBCHRONIC INHALATION STUDY OF FISCHER 344 RATS EXPOSED TO 0, 0.4, 1.4 OR 4.0 PPM ACROLEIN.

    SciTech Connect

    KUTZMAN,R.S.

    1981-10-01

    Fischer 344 rats were exposed to 0.0, 0.4, 1.4, or 4.0 ppm acrolein for 62 days. The major objective of the study was to relate the results of a series of pulmonary function tests to biochemical and pathological alterations observed in the lung. Cytological and reproductive potential endpoints were also assessed after acrolein exposure. Rats were exposed to acrolein for 6 hours/day, 5 days/week for 62 days. Mortality was observed only in the 4.0 ppm chamber where 32 of 57 exposed males died; however, none of the 8 exposed females died. Most of the mortality occurred within the first 10 exposure days. Histologic examination indicated that the animals died of acute bronchopneumonia. The surviving males and females exposed to 4.0 ppm acrolein gained weight at a significantly slower rate than control animals. The growth of both sexes in the 0.4 and 1.4 ppm groups was similar to that of their respective controls. Histopathologic examination of animals after 62 days of exposure revealed bronchiolar epithelial necrosis and sloughing, bronchiolar edema with macrophages, and focal pulmonary edema in the 4.0 ppm group. These lesions were, in some cases, associated with edema of the trachea and peribronchial lymph nodes, and acute rhinitis which indicated an upper respiratory tract effect of acrolein. Of particular interest was the variability of response between rats in the 4.0 ppm group, some not affected at all while others were moderately affected. Intragroup variability in toxicity was also apparent in the 1.4 ppm exposure group where only 3 of 31 animals examined had lesions directly related to acrolein exposure. Extra respiratory organs appeared unaffected.

  18. Use of In Vivo and In Vitro Data to Derive a Chronic Reference Value for Crotonaldehyde Based on Relative Potency to Acrolein

    PubMed Central

    Grant, Roberta L.; Jenkins, Allison F.

    2015-01-01

    The Texas Commission on Environmental Quality (TCEQ) conducted a chronic inhalation noncancer toxicity assessment for crotonaldehyde (CRO). Since there were limited toxicity data for CRO, a reference value (ReV) was derived using a relative potency factor (RPF) approach with acrolein as the index chemical. Both CRO and acrolein are α,β-unsaturated carbonyls and share common steps in their mode of action (MOA). Only studies that investigated the effects of CRO and acrolein in the same study were used to calculate a CRO:acrolein RPF. In vivo findings measuring both 50% respiratory depression in rats and two species of mice and subcutaneous 50% lethality in rats and mice were used to calculate an RPF of 3 (rounded to one significant figure). In vitro data were useful to compare the MOA of CRO and acrolein and to support the RPF determined using in vivo data. In vitro cell culture studies investigating cytotoxicity in normal human lung fibroblast cultures using the propidium iodide cytotoxicity assay and in mouse lymphocyte cultures using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) cytotoxicity assay were used to calculate an in vitro RPF of 3, which supports the in vivo RPF. The chronic ReV for acrolein of 1.2 ppb derived by TCEQ was multiplied by the RPF of 3 to calculate the ReV for CRO of 3.6 ppb (10 μg/m3). The ReV for CRO was developed to protect the general public from adverse health effects from chronic exposure to CRO in ambient air. PMID:26580244

  19. 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.

  20. Use of In Vivo and In Vitro Data to Derive a Chronic Reference Value for Crotonaldehyde Based on Relative Potency to Acrolein.

    PubMed

    Grant, Roberta L; Jenkins, Allison F

    2015-01-01

    The Texas Commission on Environmental Quality (TCEQ) conducted a chronic inhalation noncancer toxicity assessment for crotonaldehyde (CRO). Since there were limited toxicity data for CRO, a reference value (ReV) was derived using a relative potency factor (RPF) approach with acrolein as the index chemical. Both CRO and acrolein are α,β-unsaturated carbonyls and share common steps in their mode of action (MOA). Only studies that investigated the effects of CRO and acrolein in the same study were used to calculate a CRO:acrolein RPF. In vivo findings measuring both 50% respiratory depression in rats and two species of mice and subcutaneous 50% lethality in rats and mice were used to calculate an RPF of 3 (rounded to one significant figure). In vitro data were useful to compare the MOA of CRO and acrolein and to support the RPF determined using in vivo data. In vitro cell culture studies investigating cytotoxicity in normal human lung fibroblast cultures using the propidium iodide cytotoxicity assay and in mouse lymphocyte cultures using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) cytotoxicity assay were used to calculate an in vitro RPF of 3, which supports the in vivo RPF. The chronic ReV for acrolein of 1.2 ppb derived by TCEQ was multiplied by the RPF of 3 to calculate the ReV for CRO of 3.6 ppb (10 μg/m(3)). The ReV for CRO was developed to protect the general public from adverse health effects from chronic exposure to CRO in ambient air.