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Sample records for carbonylation

  1. Validation of protein carbonyl measurement

    DEFF Research Database (Denmark)

    Augustyniak, Edyta; Adam, Aisha; Wojdyla, Katarzyna;

    2015-01-01

    Protein carbonyls are widely analysed as a measure of protein oxidation. Several different methods exist for their determination. A previous study had described orders of magnitude variance that existed when protein carbonyls were analysed in a single laboratory by ELISA using different commercial...

  2. Validation of protein carbonyl measurement

    DEFF Research Database (Denmark)

    Augustyniak, Edyta; Adam, Aisha; Wojdyla, Katarzyna

    2015-01-01

    Protein carbonyls are widely analysed as a measure of protein oxidation. Several different methods exist for their determination. A previous study had described orders of magnitude variance that existed when protein carbonyls were analysed in a single laboratory by ELISA using different commercial...... kits. We have further explored the potential causes of variance in carbonyl analysis in a ring study. A soluble protein fraction was prepared from rat liver and exposed to 0, 5 and 15min of UV irradiation. Lyophilised preparations were distributed to six different laboratories that routinely undertook...... protein carbonyl analysis across Europe. ELISA and Western blotting techniques detected an increase in protein carbonyl formation between 0 and 5min of UV irradiation irrespective of method used. After irradiation for 15min, less oxidation was detected by half of the laboratories than after 5min...

  3. 49 CFR 173.198 - Nickel carbonyl.

    Science.gov (United States)

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Nickel carbonyl. 173.198 Section 173.198... Nickel carbonyl. (a) Nickel carbonyl must be packed in specification steel or nickel cylinders as prescribed for any compressed gas except acetylene. A cylinder used exclusively for nickel carbonyl may...

  4. Kinetics of the Double Carbonylation of Benzylchloride

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    It is a multi-phase-catalyzed reaction to produce calcium phenylpyruvate by double carbonylation of benzylchloride. Based on the analysis of the reaction mechanism, a kinetic model of the carbonylation reaction was obtained. The model was verified through experiments in which the diffusion effect was neglected with the appropriate operation manner. But it is inevitable that the carbonylation process is controlled by diffusion as the autoclave scaling up.

  5. Study of decomposing carbonyl slag

    Institute of Scientific and Technical Information of China (English)

    CHEN Ai-liang; SUN Pei-mei; ZHAO Zhong-wei; LI Hong-gui; CHEN Xing-yu

    2006-01-01

    A new technology was put forward to deal with the carbonyl slag at low acidity and low oxygen pressure in the kettle.With the orthogonal experiments for analyzing the sequence of four factors and some single factor experiments for the best conditions. The best conditions are used for extracting nickel, cobalt and copper and enriching precious metals: the cupric ion concentration is 5 g/L; and pH=6; the sulfur coefficient is 1.4; the oxygen pressure is 0.08 MPa; the time bubbling oxygen is 20 min;the ratio of liquid to solid is 8:1; the leaching time is 2 h; the heating time is 2.5 h. The leaching rates of nickel and cobalt are more than 98% and that of copper is above 97%. Nickel and cobalt can be separated efficiently from copper and precious metals from the carbonyl slag. Moreover, its leaching liquor has less copper. Nickel and cobalt can be reclaimed only once. During the whole process,the leaching rates of Au and Ag are more than 99.9%, while other precious metals are still in the residue without any loss.

  6. Surface decorated platinum carbonyl clusters

    Science.gov (United States)

    Ciabatti, Iacopo; Femoni, Cristina; Iapalucci, Maria Carmela; Longoni, Giuliano; Zacchini, Stefano; Zarra, Salvatore

    2012-06-01

    Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters.Four molecular Pt-carbonyl clusters decorated by Cd-Br fragments, i.e., [Pt13(CO)12{Cd5(μ-Br)5Br2(dmf)3}2]2- (1), [Pt19(CO)17{Cd5(μ-Br)5Br3(Me2CO)2}{Cd5(μ-Br)5Br(Me2CO)4}]2- (2), [H2Pt26(CO)20(CdBr)12]8- (3) and [H4Pt26(CO)20(CdBr)12(PtBr)x]6- (4) (x = 0-2), have been obtained from the reactions between [Pt3n(CO)6n]2- (n = 2-6) and CdBr2.H2O in dmf at 120 °C. The structures of these molecular clusters with diameters of 1.5-2 nm have been determined by X-ray crystallography. Both 1 and 2 are composed of icosahedral or bis-icosahedral Pt-CO cores decorated on the surface by Cd-Br motifs, whereas 3 and 4 display a cubic close packed Pt26Cd12 metal frame decorated by CO and Br ligands. An oversimplified and unifying approach to interpret the electron count of these surface decorated platinum carbonyl clusters is suggested, and extended to other low-valent organometallic clusters and Au-thiolate nanoclusters. CCDC 867747 and 867748. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr30400g

  7. Trifluoromethylation of Carbonyl Compounds with Sodium Trifluoroacetate

    Institute of Scientific and Technical Information of China (English)

    2005-01-01

    In the presence of copper (Ⅰ) halide as catalyst, a variety of carbonyl compounds could be trifluoromethylated with sodium trifluoroacetate to give the corresponding alcohols in moderate to high yields.

  8. Ab Initio MO Studies on the Reaction Mechanism for Carbonyl Insertion Catalyzed by Carbonyl Cobalt Complex

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Ab initio method, under the effective core potential(ECP) approximation at HF/LANL2DZ level, has been employed to study the reaction mechanism of the carbonyl insertion of olefin hydroformylation catalyzed by a carbonyl cobalt HCo(CO)3. The two reaction paths have been discussed. The calculated potential energy barriers for the carbonyl migration and the ethyl group migration are 105.0 kJ/mol and 39.17 kJ/mol, respectively. The results indicate that the reaction path via ethyl migration is more energetically favorable than that via carbonyl insertion.

  9. Pattern of occurrence and occupancy of carbonylation sites in proteins

    DEFF Research Database (Denmark)

    Rao, R Shyama Prasad; Møller, Ian Max

    2011-01-01

    Proteins are targets for modification by reactive oxygen species, and carbonylation is an important irreversible modification that increases during oxidative stress. While information on protein carbonylation is accumulating, its pattern is not yet understood. We have made a meta......-analysis of the available literature data (456 carbonylation sites on 208 proteins) to appreciate the nature of carbonylation sites in proteins. Of the carbonylated (Arg, Lys, Pro, and Thr – RKPT) amino acids, Lys is the most abundant, whereas Pro is the most susceptible and Thr is the least susceptible. The incidence...... of carbonylation is lower in the N-terminal part of the protein primary sequence. Although a significantly higher number of carbonylated sites occur in Arg-, Lys-, Pro- and Thr-rich regions of proteins, the hydropathy environment of carbonylated sites is not significantly different from potential carbonylation...

  10. Carbonyl compounds indoors in a changing climate

    Directory of Open Access Journals (Sweden)

    Brimblecombe Peter

    2012-03-01

    Full Text Available Abstract Background Formic acid, acetic acid and formaldehyde are important compounds in the indoor environment because of the potential for these acids to degrade calcareous materials (shells, eggs, tiles and geological specimens, paper and corrode or tarnish metals, especially copper and lead. Carbonyl sulfide tarnishes both silver and copper encouraging the formation of surface sulfides. Results Carbonyls are evolved more quickly at higher temperatures likely in the Cartoon Gallery at Knole, an important historic house near Sevenoaks in Kent, England where the study is focused. There is a potential for higher concentrations to accumulate. However, it may well be that in warmer climates they will be depleted more rapidly if ventilation increases. Conclusions Carbonyls are likely to have a greater impact in the future.

  11. Millimeter wave spectra of carbonyl cyanide ⋆

    Science.gov (United States)

    Bteich, S.B.; Tercero, B.; Cernicharo, J.; Motiyenko, R.A.; Margulès, L.; Guillemin, J.-C.

    2016-01-01

    Context More than 30 cyanide derivatives of simple organic molecules have been detected in the interstellar medium, but only one dicarbonitrile has been found and that very recently. There is still a lack of high-resolution spectroscopic data particularly for dinitriles derivatives. The carbonyl cyanide molecule is a new and interesting candidate for astrophysical detection. It could be formed by the reaction of CO and CN radicals, or by substitution of the hydrogen atom by a cyano group in cyanoformaldehyde, HC(=O)CN, that has already been detected in the interstellar medium. Aims The available data on the rotational spectrum of carbonyl cyanide is limited in terms of quantum number values and frequency range, and does not allow accurate extrapolation of the spectrum into the millimeter-wave range. To provide a firm basis for astrophysical detection of carbonyl cyanide we studied its millimeter-wave spectrum. Methods The rotational spectrum of carbonyl cyanide was measured in the frequency range 152 - 308 GHz and analyzed using Watson’s A- and S-reduction Hamiltonians. Results The ground and first excited state of v5 vibrational mode were assigned and analyzed. More than 1100 distinct frequency lines of the ground state were fitted to produce an accurate set of rotational and centrifugal distortion constants up to the eighth order. The frequency predictions based on these constants should be accurate enough for astrophysical searches in the frequency range up to 500 GHz and for transition involving energy levels with J ≤ 100 and Ka ≤ 42. Based on the results we searched for interstellar carbonyl cyanide in available observational data without success. Thus, we derived upper limits to its column density in different sources. PMID:27738349

  12. Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2013-01-01

    A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts satisfact......A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts...... by the competition between chain‐branching and ‐propagating steps; modeling predictions are particularly sensitive to the branching fraction for the OCS + O reaction to form CO + SO or CO2 + S....

  13. Carbonyl compounds generated from electronic cigarettes.

    Science.gov (United States)

    Bekki, Kanae; Uchiyama, Shigehisa; Ohta, Kazushi; Inaba, Yohei; Nakagome, Hideki; Kunugita, Naoki

    2014-10-28

    Electronic cigarettes (e-cigarettes) are advertised as being safer than tobacco cigarettes products as the chemical compounds inhaled from e-cigarettes are believed to be fewer and less toxic than those from tobacco cigarettes. Therefore, continuous careful monitoring and risk management of e-cigarettes should be implemented, with the aim of protecting and promoting public health worldwide. Moreover, basic scientific data are required for the regulation of e-cigarette. To date, there have been reports of many hazardous chemical compounds generated from e-cigarettes, particularly carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, and glyoxal, which are often found in e-cigarette aerosols. These carbonyl compounds are incidentally generated by the oxidation of e-liquid (liquid in e-cigarette; glycerol and glycols) when the liquid comes in contact with the heated nichrome wire. The compositions and concentrations of these compounds vary depending on the type of e-liquid and the battery voltage. In some cases, extremely high concentrations of these carbonyl compounds are generated, and may contribute to various health effects. Suppliers, risk management organizations, and users of e-cigarettes should be aware of this phenomenon.

  14. Carbonyl Compounds Generated from Electronic Cigarettes

    Directory of Open Access Journals (Sweden)

    Kanae Bekki

    2014-10-01

    Full Text Available Electronic cigarettes (e-cigarettes are advertised as being safer than tobacco cigarettes products as the chemical compounds inhaled from e-cigarettes are believed to be fewer and less toxic than those from tobacco cigarettes. Therefore, continuous careful monitoring and risk management of e-cigarettes should be implemented, with the aim of protecting and promoting public health worldwide. Moreover, basic scientific data are required for the regulation of e-cigarette. To date, there have been reports of many hazardous chemical compounds generated from e-cigarettes, particularly carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, and glyoxal, which are often found in e-cigarette aerosols. These carbonyl compounds are incidentally generated by the oxidation of e-liquid (liquid in e-cigarette; glycerol and glycols when the liquid comes in contact with the heated nichrome wire. The compositions and concentrations of these compounds vary depending on the type of e-liquid and the battery voltage. In some cases, extremely high concentrations of these carbonyl compounds are generated, and may contribute to various health effects. Suppliers, risk management organizations, and users of e-cigarettes should be aware of this phenomenon.

  15. Carbonyl Emissions from Gasoline and Diesel Motor Vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Destaillats, Hugo; Jakober, Chris A.; Robert, Michael A.; Riddle, Sarah G.; Destaillats, Hugo; Charles, M. Judith; Green, Peter G.; Kleeman, Michael J.

    2007-12-01

    Carbonyls from gasoline powered light-duty vehicles (LDVs) and heavy-duty diesel powered vehicles (HDDVs) operated on chassis dynamometers were measured using an annular denuder-quartz filter-polyurethane foam sampler with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization and chromatography-mass spectrometry analyses. Two internal standards were utilized based on carbonyl recovery, 4-fluorobenzaldehyde forcarbonyls and 6-fluoro-4-chromanone for>_C8 compounds. Gas- and particle-phase emissions for 39 aliphatic and 20 aromatic carbonyls ranged from 0.1 ? 2000 ?g/L fuel for LDVs and 1.8 - 27000 mu g/L fuel for HDDVs. Gas-phase species accounted for 81-95percent of the total carbonyls from LDVs and 86-88percent from HDDVs. Particulate carbonyls emitted from a HDDV under realistic driving conditions were similar to concentrations measured in a diesel particulate matter (PM) standard reference material. Carbonyls accounted for 19percent of particulate organic carbon (POC) emissions from low-emission LDVs and 37percent of POC emissions from three-way catalyst equipped LDVs. This identifies carbonyls as one of the largest classes of compounds in LDV PM emissions. The carbonyl fraction of HDDV POC was lower, 3.3-3.9percent depending upon operational conditions. Partitioning analysis indicates the carbonyls had not achieved equilibrium between the gas- and particle-phase under the dilution factors of 126-584 used in the current study.

  16. Acute inhalation toxicity of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Benson, J.M.; Hahn, F.F.; Barr, E.B. [and others

    1995-12-01

    Carbonyl sulfide (COS), a colorless gas, is a side product of industrial procedures sure as coal hydrogenation and gasification. It is structurally related to and is a metabolite of carbon disulfide. COS is metabolized in the body by carbonic anhydrase to hydrogen sulfide (H{sub 2}S), which is thought to be responsible for COS toxicity. No threshold limit value for COS has been established. Results of these studies indicate COS (with an LC{sub 50} of 590 ppm) is slightly less acutely toxic than H{sub 2}S (LC{sub 50} of 440 ppm).

  17. Pollution survey of carbonyl compounds in train air

    Institute of Scientific and Technical Information of China (English)

    LU Hao; ZHU Lizhong

    2007-01-01

    The train iS an important vehicle in China,but its air quality has important impacts on passengers' health.In this work,pollution from carbonyl compounds was measured in the air of six trains.The obiectives of this work were to investigate carbonyl compound levels in selected air from trains,identify their emission sources,and assess the intake of carbonyl compounds for passengers.The methods for sampling and analyzing 10 carbonyl compounds such as formaldehyde,acetaldehyde,acrolein,acetone,propionalde hyde,crotonaldehyde,butyraldehyde,benzaldehyde,cyclo hexanone,and valeraldehyde in indoor air were proposed with the sampling efficiency,recovery,and detection limit being 92%-100%,91%-104%,and 0.26-0.82 ng/m3,respec tively.It was indicated that the total concentrations of carbonyl compounds were 0.159-0.2828 mg/m3 with the average concentration of 0.2330 mg/m3.The average concen trations of formaldehyde.acetaldehyde and acetone were 0.0922,0.0499,and 0.0580 mg/m3,accounting for 42.6%,21.4%.and 24.9% of the total concentrations of carbonyl compounds,respectively.The carbonyl compounds probably came from woodwork and cigarette smoking.The intake of carbonyl compounds for the passengers was approximately 0.043-0.076 mg/h.The carbonyl compounds in train air could be harmful to human health.

  18. Effect of hydrogen atoms on the structures of trinuclear metal carbonyl clusters: trinuclear manganese carbonyl hydrides.

    Science.gov (United States)

    Liu, Xian-mei; Wang, Chao-yang; Li, Qian-shu; Xie, Yaoming; King, R Bruce; Schaefer, Henry F

    2009-05-18

    The structures of the trinuclear manganese carbonyl hydrides H(3)Mn(3)(CO)(n) (n = 12, 11, 10, 9) have been investigated by density functional theory (DFT). Optimization of H(3)Mn(3)(CO)(12) gives the experimentally known structure in which all carbonyl groups are terminal and each edge of a central Mn(3) equilateral triangle is bridged by a single hydrogen atom. This structure establishes the canonical distance 3.11 A for the Mn-Mn single bond satisfying the 18-electron rule. The central triangular (mu-H)(3)Mn(3) unit is retained in the lowest energy structure of H(3)Mn(3)(CO)(11), which may thus be derived from the H(3)Mn(3)(CO)(12) structure by removal of a carbonyl group with concurrent conversion of one of the remaining carbonyl groups into a semibridging carbonyl group to fill the resulting hole. The potential energy surface of H(3)Mn(3)(CO)(10) is relatively complicated with six singlet and five triplet structures. One of the lower energy H(3)Mn(3)(CO)(10) structures has one of the hydrogen atoms bridging the entire Mn(3) triangle and the other two hydrogen atoms bridging Mn-Mn edges. This H(3)Mn(3)(CO)(10) structure achieves the favored 18-electron configuration with a very short MnMn triple bond of 2.36 A. The other low energy H(3)Mn(3)(CO)(10) structure retains the (mu-H)(3)Mn(3) core of H(3)Mn(3)(CO)(12) but has a unique six-electron donor eta(2)-mu(3) carbonyl group bridging the entire Mn(3) triangle similar to the unique carbonyl group in the known compound Cp(3)Nb(3)(CO)(6)(eta(2)-mu(3)-CO). For H(3)Mn(3)(CO)(9) a structure with a central (mu(3)-H)(2)Mn(3) trigonal bipyramid lies >20 kcal/mol below any of the other structures. Triplet structures were found for the unsaturated H(3)Mn(3)(CO)(n) (n = 11, 10, 9) systems but at significantly higher energies than the lowest lying singlet structures.

  19. Carbonyl sulfide: No remedy for global warming

    Science.gov (United States)

    Taubman, Steven J.; Kasting, James F.

    1995-04-01

    The enhancement of the stratospheric aerosol layer caused by the eruption of Mt. Pinatubo (June 15, 1991), and the subsequent cooling of the earth's lower atmosphere [Dutton and Christy, 1992; Minnis et al., 1993] shows that stratospheric aerosols can have a strong effect on the earth's climate. This supports the notion that the intentional enhancement of the stratospheric aerosol layer through increased carbonyl sulfide (OCS) emissions might be an effective means for counteracting global warming. Through the use of a one-dimensional photochemical model, we investigate what effect such a program might have on global average stratospheric ozone. In addition, we consider the impact of enhanced OCS emissions on rainwater acidity and on the overall health of both plants and animals. We find that while the warming produced by a single CO2 doubling (1 to 4°C) might be offset with ozone losses of less than 5%, any attempt to use carbonyl sulfide as a permanent solution to global warming could result in depletion of global average ozone by 30% or more. We estimate that in order to achieve cooling of 4°C rainwater pH would fall to between 3.5 and 3.8. Finally, a 4°C cooling at the surface will require that ambient near ground OCS levels rise to above 10 ppmv which is probably greater than the safe exposure limit for humans. Thus, enhanced OCS emissions do not provide an environmentally acceptable solution to the problem of global warming.

  20. Characterization of oxidative carbonylation on recombinant monoclonal antibodies.

    Science.gov (United States)

    Yang, Yi; Stella, Cinzia; Wang, Weiru; Schöneich, Christian; Gennaro, Lynn

    2014-05-20

    In the biotechnology industry, oxidative carbonylation as a post-translational modification of protein pharmaceuticals has not been studied in detail. Using Quality by Design (QbD) principles, understanding the impact of oxidative carbonylation on product quality of protein pharmaceuticals, particularly from a site-specific perspective, is critical. However, comprehensive identification of carbonylation sites has so far remained a very difficult analytical challenge for the industry. In this paper, we report for the first time the identification of specific carbonylation sites on recombinant monoclonal antibodies with a new analytical approach via derivatization with Girard's Reagent T (GRT) and subsequent peptide mapping with high-resolution mass spectrometry. Enhanced ionization efficiency and high quality MS(2) data resulted from GRT derivatization were observed as key benefits of this approach, which enabled direct identification of carbonylation sites without any fractionation or affinity enrichment steps. A simple data filtering process was also incorporated to significantly reduce false positive assignments. Sensitivity and efficiency of this approach were demonstrated by identification of carbonylation sites on both unstressed and oxidized antibody bulk drug substances. The applicability of this approach was further demonstrated by identification of 14 common carbonylation sites on three highly similar IgG1s. Our approach represents a significant improvement to the existing analytical methodologies and facilitates extended characterization of oxidative carbonylation on recombinant monoclonal antibodies and potentially other protein pharmaceuticals in the biotechnology industry.

  1. Synthesis of main-chain metal carbonyl organometallic macromolecules (MCMCOMs).

    Science.gov (United States)

    Cao, Kai; Murshid, Nimer; Wang, Xiaosong

    2015-04-01

    Synthesis of main-chain metal carbonyl organometallic macromolecules (MCMCOMs) is difficult, mainly due to the instability of metal carbonyl complexes. Despite its challenge a number of MCMCOMs has been prepared by strategically using organometallic, organic, and polymer synthetic chemistry. Main contributions to this research field were reported by the groups of Tyler, Pannell, and Wang and are briefly summarized in this article.

  2. Bifunctional dendrons for multiple carbohydrate presentation via carbonyl chemistry

    Directory of Open Access Journals (Sweden)

    Davide Bini

    2014-07-01

    Full Text Available The synthesis of new dendrons of the generations 0, 1 and 2 with a double bond at the focal point and a carbonyl group at the termini has been carried out. The carbonyl group has been exploited for the multivalent conjugation to a sample saccharide by reductive amination and alkoxyamine conjugation.

  3. Carbonyl-Olefin Exchange Reaction: Present State and Outlook

    Science.gov (United States)

    Kalinova, Radostina; Jossifov, Christo

    The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

  4. Metal-free carbonylations by photoredox catalysis.

    Science.gov (United States)

    Majek, Michal; Jacobi von Wangelin, Axel

    2015-02-01

    The synthesis of benzoates from aryl electrophiles and carbon monoxide is a prime example of a transition-metal-catalyzed carbonylation reaction which is widely applied in research and industrial processes. Such reactions proceed in the presence of Pd or Ni catalysts, suitable ligands, and stoichiometric bases. We have developed an alternative procedure that is free of any metal, ligand, and base. The method involves a redox reaction driven by visible light and catalyzed by eosin Y which affords alkyl benzoates from arene diazonium salts, carbon monoxide, and alcohols under mild conditions. Tertiary esters can also be prepared in high yields. DFT calculations and radical trapping experiments support a catalytic photoredox pathway without the requirement for sacrificial redox partners.

  5. Catalyst Initiation in the Oscillatory Carbonylation Reaction

    Directory of Open Access Journals (Sweden)

    Katarina Novakovic

    2011-01-01

    Full Text Available Palladium(II iodide is used as a catalyst in the phenylacetylene oxidative carbonylation reaction that has demonstrated oscillatory behaviour in both pH and heat of reaction. In an attempt to extract the reaction network responsible for the oscillatory nature of this reaction, the system was divided into smaller parts and they were studied. This paper focuses on understanding the reaction network responsible for the initial reactions of palladium(II iodide within this oscillatory reaction. The species researched include methanol, palladium(II iodide, potassium iodide, and carbon monoxide. Several chemical reactions were considered and applied in a modelling study. The study revealed the significant role played by traces of water contained in the standard HPLC grade methanol used.

  6. High throughput assay for evaluation of reactive carbonyl scavenging capacity

    Directory of Open Access Journals (Sweden)

    N. Vidal

    2014-01-01

    Full Text Available Many carbonyl species from either lipid peroxidation or glycoxidation are extremely reactive and can disrupt the function of proteins and enzymes. 4-hydroxynonenal and methylglyoxal are the most abundant and toxic lipid-derived reactive carbonyl species. The presence of these toxics leads to carbonyl stress and cause a significant amount of macromolecular damages in several diseases. Much evidence indicates trapping of reactive carbonyl intermediates may be a useful strategy for inhibiting or decreasing carbonyl stress-associated pathologies. There is no rapid and convenient analytical method available for the assessment of direct carbonyl scavenging capacity, and a very limited number of carbonyl scavengers have been identified to date, their therapeutic potential being highlighted only recently. In this context, we have developed a new and rapid sensitive fluorimetric method for the assessment of reactive carbonyl scavengers without involvement glycoxidation systems. Efficacy of various thiol- and non-thiol-carbonyl scavenger pharmacophores was tested both using this screening assay adapted to 96-well microplates and in cultured cells. The scavenging effects on the formation of Advanced Glycation End-product of Bovine Serum Albumin formed with methylglyoxal, 4-hydroxynonenal and glucose-glycated as molecular models were also examined. Low molecular mass thiols with an α-amino-β-mercaptoethane structure showed the highest degree of inhibitory activity toward both α,β-unsaturated aldehydes and dicarbonyls. Cysteine and cysteamine have the best scavenging ability toward methylglyoxal. WR-1065 which is currently approved for clinical use as a protective agent against radiation and renal toxicity was identified as the best inhibitor of 4-hydroxynonenal.

  7. 16th Carbonyl Metabolism Meeting: from enzymology to genomics

    Directory of Open Access Journals (Sweden)

    Maser Edmund

    2012-12-01

    Full Text Available Abstract The 16th International Meeting on the Enzymology and Molecular Biology of Carbonyl Metabolism, Castle of Ploen (Schleswig-Holstein, Germany, July 10–15, 2012, covered all aspects of NAD(P-dependent oxido-reductases that are involved in the general metabolism of xenobiotic and physiological carbonyl compounds. Starting 30 years ago with enzyme purification, structure elucidation and enzyme kinetics, the Carbonyl Society members have meanwhile established internationally recognized enzyme nomenclature systems and now consider aspects of enzyme genomics and enzyme evolution along with their roles in diseases. The 16th international meeting included lectures from international speakers from all over the world.

  8. A New HPLC Method to Determine Carbonyl Compounds in Air

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    In this paper, a new HPLC method was established to determine the carbonyl compounds in air. As the absorbent, 2, 4-dinitrophenylhydrazine (2, 4-DNPH) reacted with carbonyls specifically, which form the corresponding 2,4-dinitrophenylhydrazones, then analyzed by HPLC. The chromatographic conditions, the recovery rate, stability of samples, reagent blank, sampling efficiency were all studied systematically. The results showed that this established method had high sensitivity and good selectivity compared with other analytical methods, and it can determine ten carbonyl compounds in air in 26 min simultaneously.

  9. Deposition of carbonyl sulphide to soils

    Science.gov (United States)

    Kluczewski, S. M.; Brown, K. A.; Bel, J. N. B.

    Carbonyl sulphide (COS) is a trace constituent of the atmosphere and is also the main form in which 35S is released from CO 2-cooled nuclear reactors. Measurements of its deposition velocity ( Vg) are therefore important for validating radiological dose models and for interpreting the role of COS in the global S cycle. The Vg of [ 35S]COS to thin layers of several contrasting soils was measured in a through-flow fumigation system. Deposition velocity was not significantly affected by soil type, although deposition to moist soil was significantly greater ( P dried soils, mean values being 5.71 × 10 -6 ms -1 and 3.06 × 10 -6 ms -1, respectively. The results obtained are about three orders of magnitude smaller than published Vg values for SO 2 to similar soils, which suggests that uptake by soils is not a major sink for atmospheric COS. The results are consistent with the hypothesis that deposition to soil of [ 35S]COS from nuclear reactors is unlikely to contribute significantly to radiation dose from the food chain pathway. The reduction in Vg observed in heat-treated soils indicates a microbial involvement in uptake. However, it seems unlikely that microbial metabolism is the rate-controlling step, since stimulation of the microflora by the addition of nutrients did not increase COS deposition.

  10. Theoretical Estimate of Hydride Affinities of Aromatic Carbonyl Compounds

    Institute of Scientific and Technical Information of China (English)

    AI Teng; ZHU Xiao-Qing; CHENG Jin-Pei

    2003-01-01

    @@ Aromatic carbonyl compounds are one type of the most important organic compounds, and the reductions ofthem by hydride agents such as LiAlH4 or NaBH4 are widely used in organic synthesis. The reactivity of carbonyl compounds generally increases in the following order: ketone < aldehyde, and amide < acid < ester < acid halide, which could be related to their hydride affinities (HA). In the previous paper, Robert[1] calculated the absolute HAof a series of small non-aromatic carbonyl compounds. In this paper, we use DFT method at B3LYP/6-311 + + G (2d, 2p)∥B3LYP/6-31 + G* level to estimate hydride affinities of five groups of aromatic carbonyl compounds. The detailed results are listed in Table 1.

  11. Carbonyl-Olefin Exchange Reaction and Related Chemistry

    Science.gov (United States)

    Jossifov, Christo; Kalinova, Radostina

    A new carbon—carbon double bond forming reaction (carbonyl olefin exchange reaction) mediated by transition metal catalytic systems has been discovered. The catalytic systems used (transition metal halides or oxohalides alone or in combination with Lewis acids) are active only in the case when the two reacting groups are in one molecules and are conjugated. In addition these systems accelerate other reactions which run simultaneously with the carbonyl olefin metathesis rendering a detailed investigation of the process very complicated.

  12. DNA damage by carbonyl stress in human skin cells

    Energy Technology Data Exchange (ETDEWEB)

    Roberts, Michael J.; Wondrak, Georg T.; Laurean, Daniel Cervantes; Jacobson, Myron K.; Jacobson, Elaine L

    2003-01-28

    Reactive carbonyl species (RCS) are potent mediators of cellular carbonyl stress originating from endogenous chemical processes such as lipid peroxidation and glycation. Skin deterioration as observed in photoaging and diabetes has been linked to accumulative protein damage from glycation, but the effects of carbonyl stress on skin cell genomic integrity are ill defined. In this study, the genotoxic effects of acute carbonyl stress on HaCaT keratinocytes and CF3 fibroblasts were assessed. Administration of the {alpha}-dicarbonyl compounds glyoxal and methylglyoxal as physiologically relevant RCS inhibited skin cell proliferation, led to intra-cellular protein glycation as evidenced by the accumulation of N{sup {epsilon}}-(carboxymethyl)-L-lysine (CML) in histones, and caused extensive DNA strand cleavage as assessed by the comet assay. These effects were prevented by treatment with the carbonyl scavenger D-penicillamine. Both glyoxal and methylglyoxal damaged DNA in intact cells. Glyoxal caused DNA strand breaks while methylglyoxal produced extensive DNA-protein cross-linking as evidenced by pronounced nuclear condensation and total suppression of comet formation. Glycation by glyoxal and methylglyoxal resulted in histone cross-linking in vitro and induced oxygen-dependent cleavage of plasmid DNA, which was partly suppressed by the hydroxyl scavenger mannitol. We suggest that a chemical mechanism of cellular DNA damage by carbonyl stress occurs in which histone glycoxidation is followed by reactive oxygen induced DNA stand breaks. The genotoxic potential of RCS in cultured skin cells and its suppression by a carbonyl scavenger as described in this study have implications for skin damage and carcinogenesis and its prevention by agents selective for carbonyl stress.

  13. Carbonyl species characteristics during the evaporation of essential oils

    Science.gov (United States)

    Chiang, Hsiu-Mei; Chiu, Hua-Hsien; Lai, Yen-Ming; Chen, Ching-Yen; Chiang, Hung-Lung

    2010-06-01

    Carbonyls emitted from essential oils can affect the air quality when they are used in indoors, especially under poor ventilation conditions. Lavender, lemon, rose, rosemary, and tea tree oils were selected as typical and popular essential oils to investigate in terms of composition, thermal characteristics and fifteen carbonyl constituents. Based on thermogravimetric (TG) analysis, the activation energy was 7.6-8.3 kcal mol -1, the reaction order was in the range of 0.6-0.7 and the frequency factor was 360-2838 min -1. Formaldehyde, acetaldehyde, acetone, and propionaldehyde were the dominant carbonyl compounds, and their concentrations were 0.034-0.170 ppm. The emission factors of carbonyl compounds were 2.10-3.70 mg g -1, and acetone, propionaldehyde, acetaldehyde, and formaldehyde accounted for a high portion of the emission factor of carbonyl compounds in essential oil exhaust. Some unhealthy carbonyl species such as formaldehyde and valeraldehyde, were measured at low-temperature during the vaporization of essential oils, indicating a potential effect on indoor air quality and human health.

  14. Determination of Carbonyl Compounds in Exhaled Cigarette Smoke

    Directory of Open Access Journals (Sweden)

    Moldoveanu S

    2014-12-01

    Full Text Available This paper presents the findings on a quantitative evaluation of carbonyl levels in exhaled cigarette smoke from human subjects. The cigarettes evaluated include products with 5.0 mg ‘tar’, 10.6 mg ‘tar’ and 16.2 mg ‘tar’, where ‘tar’ is defined as the weight of total wet particulate matter (TPM minus the weight of nicotine and water, and the cigarettes are smoked following U.S. Federal Trade Commission (FTC recommendations. The measured levels of carbonyls in the exhaled smoke were compared with calculated yields of carbonyls in the inhaled smoke and a retention efficiency was obtained. The number of human subjects included a total of ten smokers for the 10.6 mg ‘tar’, five for the 16.2 mg ‘tar’, and five for the 5.0 mg ‘tar’ product, each subject smoking three cigarettes. The analyzed carbonyl compounds included several aldehydes (formaldehyde, acetaldehyde, acrolein, propionaldehyde, crotonaldehyde and n-butyraldehyde, and two ketones (acetone and 2-butanone. The smoke collection from the human subjects was vacuum assisted. Exhaled smoke was collected on Cambridge pads pretreated with a solution of dinitrophenylhydrazine (DNPH followed by high performance liquid chromatography (HPLC analysis of the dinitrophenylhydrazones of the carbonyl compounds. The cigarette butts from the smokers were collected and analyzed for nicotine. The nicotine levels for the cigarette butts from the smokers were used to calculate the level of carbonyls in the inhaled smoke, based on calibration curves. These were generated separately by analyzing the carbonyls in smoke and the nicotine in the cigarette butts obtained by machine smoking under different puffing regimes. The comparison of the level of carbonyl compounds in exhaled smoke with that from the inhaled smoke showed high retention of all the carbonyls. The retention of aldehydes was above 95% for all three different ‘tar’ levels cigarettes. The ketones were retained with a

  15. New methodology for removing carbonyl compounds from sweet wines.

    Science.gov (United States)

    Blasi, Mélanie; Barbe, Jean-Christophe; Maillard, Bernard; Dubourdieu, Denis; Deleuze, Hervé

    2007-12-12

    Sweet white wines from botrytized grapes present high SO2 levels because of their high sulfur dioxide binding power. The objective of this work was to develop a new method for reducing this binding power by partially eliminating the carbonyl compounds naturally present in these wines that are responsible for this phenomenon. A selective liquid-solid removal technique was developed. Phenylsulfonylhydrazine was selected as the best candidate for removing carbonyl compounds. Its reactivity in the presence or absence of sulfur dioxide was verified in model media containing acetaldehyde, pyruvic acid, and 2-oxoglutaric acid, some of the main carbonyl compounds responsible for the SO2 binding power of sweet wines. The scavenging function was grafted on porous polymer supports, and its efficiency was evaluated in model wines. Dependent upon the supports used, different quantities of carbonyl compounds (over 90% in some cases) were removed in a few days. The presence of sulfur dioxide delayed removal without changing its quality. The results obtained showed that the method removed carbonyl compounds efficiently and was applicable to wines at any stage in winemaking.

  16. Carbonyl Sulfides as Possible Intermediates in the Photolysis of Oxathiiranes

    DEFF Research Database (Denmark)

    Carlsen, Lars; Snyder, J. P.; Holm, A.

    1981-01-01

    of sulfine to ketone via the oxathiirane and the subsequent blue intermediate implies the absence of triplet and biradical singlet transients. The unknown carbonyl sulfide functionality, R2C&z.dbnd;O&z.dbnd;S, thereby emerges as a strong candidate for producing the visible absorption. Comparison of the wave...... functions for CH2&z.dbnd;S&z.dbnd;O and CH2&z.dbnd;O&z.dbnd;S arising from MNDO limited CI geometry optimizations leads to the conclusion that the carbonyl sulfide structure is best described as a zwitterion rather than as a singlet biradical. The failure to observe cycloaddition products between the blue...

  17. An alternative method for monitoring carbonyls, and the development of a 24-port fully automated carbonyl sampler for PAMS program

    Energy Technology Data Exchange (ETDEWEB)

    Parmar, S.S.; Ugarova, L. [Atmospheric Analysis and Consulting, Ventura, CA (United States); Fernandes, C.; Guyton, J.; Lee, C.P. [Arizona Dept. of Environmental Quality, Phoenix, AZ (United States)

    1994-12-31

    The authors have investigated the possibility of collecting different aldehydes and ketones on different sorbents such as silica gel, molecular sieve and charcoal followed by solvent extraction, DNPH derivatization and HPLC/UV analysis. Carbonyl collection efficiencies for these sorbents were calculated relative to a DNPH coated C{sub 18} sep-pak cartridge. From a limited number of laboratory experiments, at various concentrations, it appears that silica gel tubes can be used for sampling aldehydes (collection efficiencies {approximately} 1), whereas charcoal tubes are suitable for collecting ketones. Molecular sieve was found to be unsuitable for collecting most of the carbonyl studied. The authors also report the development of a fully automated 24-port carbonyl sampler specially designed for EPA`s PAMS program.

  18. Age-related variations of protein carbonyls in human saliva and plasma: is saliva protein carbonyls an alternative biomarker of aging?

    Science.gov (United States)

    Wang, Zhihui; Wang, Yanyi; Liu, Hongchen; Che, Yuwei; Xu, Yingying; E, Lingling

    2015-06-01

    Free radical hypothesis which is one of the most acknowledged aging theories was developed into oxidative stress hypothesis. Protein carbonylation is by far one of the most widely used markers of protein oxidation. We studied the role of age and gender in protein carbonyl content of saliva and plasma among 273 Chinese healthy subjects (137 females and 136 males aged between 20 and 79) and discussed the correlation between protein carbonyl content of saliva and plasma. Protein carbonyl content of saliva and plasma were, respectively, 2.391 ± 0.639 and 0.838 ± 0.274 nmol/mg. Variations of saliva and plasma different age groups all reached significant differences in both male and female (all p saliva and plasma protein carbonyls were found to be significantly correlated with age (r = 0.6582 and r = 0.5176, all p saliva and plasma protein carbonyl levels (all p > 0.05). Saliva and plasma protein carbonyls were positively related (r = 0.4405, p saliva and plasma protein carbonyls/ferric reducing ability of plasma (FRAP) ratios were proved to be significantly correlated with age (r = 0.7796 and r = 0.6938, all p saliva protein carbonyls/FRAP ratio and plasma protein carbonyls/FRAP ratio were also correlated (r = 0.5573, p saliva protein carbonyls seem to be an alternative biomarker of aging while the mechanisms of protein carbonylation and oxidative stress and the relationship between saliva protein carbonyls and diseases need to be further investigated.

  19. α-Carbonyl Radical Cyclizatio n in Organic Synthesis

    Institute of Scientific and Technical Information of China (English)

    SHA Chin-Kang; CHIU Rei-Torng; LIH Shinn-Horng; SANTHOSH K. C.; CHANG Ching-Jung; TSENG Wei-Hong; HO Wen-Yueh

    2001-01-01

    @@ Intramolecular radical cyclization reactions are now used routinely to synthesize carbocyclic and heterocyclic structures. We have reported that α-carbonyl radicals 1, generated from the corresponding iodo ketones or enones, underwent intramolecular radical cyclization smoothly to afford products 2.1, 2,3

  20. Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

    Science.gov (United States)

    Rathke, Jerome W.; Klingler, Robert J.

    1993-01-01

    A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

  1. Comparing Carbonyl Chemistry in Comprehensive Introductory Organic Chemistry Textbooks

    Science.gov (United States)

    Nelson, Donna J.; Kumar, Ravi; Ramasamy, Saravanan

    2015-01-01

    Learning the chemistry of compounds containing carbonyl groups is difficult for undergraduate students partly because of a convolution of multiple possible reaction sites, competitive reactions taking place at those sites, different criteria needed to discern between the mechanisms of these reactions, and no straightforward selection method…

  2. Efficient Nd Promoted Rh Catalysts for Vapor Phase Methanol Carbonylation

    Institute of Scientific and Technical Information of China (English)

    Shu Feng ZHANG; Qing Li QIAN; Ping Lai PAN; Yi CHEN; Guo Qing YUAN

    2005-01-01

    A Nd promoted-Rh catalysts supported on polymer-derived carbon beads for vapor-phase methanol carbonylation was developed. Rh-Nd bimetallic catalysts obviously have higher activity than that of supported Rh catalyst under similar reaction condition. The difference between the activity of above two catalyst systems is clearly caused by the intrinsic properties generated by the introduction of Nd.

  3. Contamination of coal benzol by carbonyl compound impurities

    Energy Technology Data Exchange (ETDEWEB)

    Yakovleva, T.P.

    1985-03-01

    The origin of most carbonyl compounds in nitration-grade benzene produced from coke-oven crude benzole (causing problems in isopropylbenzene production) was concluded to be the piperylene fraction (a by-product of isoprene manufacture) used as an additive in the washing of the benzene with sulphuric acid.

  4. Metal-Diazo Radicals of α-Carbonyl Diazomethanes

    Science.gov (United States)

    Li, Feifei; Xiao, Longqiang; Liu, Lijian

    2016-03-01

    Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [RhICl(cod)]2, [CoII(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was observed in measurements of α-carbonyl diazomethane adducts of [RhICl(cod)]2 in the presence of 5,5-dimethyl-pyrroline-1-N-oxide (DMPO). DFT calculations indicated that 97.2% of spin density is localized on the diazo moiety. Co- and Pd-diazo radicals are EPR silent but were captured by DMPO to form spin adducts of DMPO-N• (triplet-of-sextets signal). The spin-trapping also provides a powerful tool for detection of metal-carbene radicals, as evidenced by the DMPO-trapped carbene radicals (DMPO-C•, sextet signal) and 2-methyl-2-nitrosopropane-carbene adducts (MNP-C•, doublet-of-triplets signal). The transformation of α-carbonyl diazomethanes to metal-carbene radicals was confirmed to be a two-step process via metal-diazo radicals.

  5. Frustrated Lewis pairs-assisted reduction of carbonyl compounds

    DEFF Research Database (Denmark)

    Marek, Ales; Pedersen, Martin Holst Friborg

    2015-01-01

    An alternative and robust method for the reduction of carbonyl groups by frustrated Lewis pairs (FLPs) is reported in this paper. With its very mild reaction conditions, good to excellent yields, absolute regioselectivity and the non-metallic character of the reagent, it provides an excellent tool...

  6. - Wave Spectrum of Carbonyl Diazide in Pursuit of Diazirinone

    Science.gov (United States)

    Amberger, Brent K.; Esselman, Brian J.; Woods, R. Claude; McMahon, Robert J.

    2013-06-01

    Pyrolysis of carbonyl diazide (CO(N_3)_2) has been shown to give diazirinone (CON_2). While diazirione decomposes over the course of a few hours under terrestrial conditions, there is the possibility for it to exist in space. In the pursuit of obtaining a rotational spectrum for diazirinone, we have started with the rotational spectroscopy of its immediate precursor, carbonyl diazide. Carbonyl diazide is highly explosive, and requires careful synthesis. Spectra in the range of 260-360 GHz were collected at room temperature and at -60°C. Ab initio calculations at the CCSD/cc-pVDZ level predict that the conformation where both azide groups are syn to the carbonyl is preferred. A second conformation, where one azide is syn and one is anti, is calculated to lie about 2 kcal/ mol higher in energy. Pure rotational transitions for the ground state and multiple low-lying excited vibrational states of the syn- syn conformation are readily observed and assigned. X. Zeng, H. Beckers, H. Willner and J. F. Stanton, Angew. Chem. Int. Ed. 50 (2011), 1720-1723 A. M. Nolan, B. K. Amberger, B. J. Esselman, V. S. Thimmakondu, J. F. Stanton, R. C. Woods, and R. J. McMahon, Inorg. Chem. 51 (2012), 9846-9851

  7. Plasma protein carbonyl levels and breast cancer risk.

    Science.gov (United States)

    Rossner, Pavel; Terry, Mary Beth; Gammon, Marilie D; Agrawal, Meenakshi; Zhang, Fang Fang; Ferris, Jennifer S; Teitelbaum, Susan L; Eng, Sybil M; Gaudet, Mia M; Neugut, Alfred I; Santella, Regina M

    2007-01-01

    To study the role of oxidative stress in breast cancer risk, we analysed plasma levels of protein carbonyls in 1050 cases and 1107 controls. We found a statistically significant trend in breast cancer risk in relation to increasing quartiles of plasma protein carbonyl levels (OR = 1.2, 95% CI = 0.9-1.5; OR = 1.5, 95% CI = 1.2-2.0; OR = 1.6, 95% CI = 1.2-2.1, for the 2(nd), 3(rd) and 4(th) quartile relative to the lowest quartile, respectively, P for trend = 0.0001). The increase in risk was similar for younger ( or = 15 grams/day for 4(th) quartile versus lowest quartile OR = 2.3, 95% CI = 1.1-4.7), and hormone replacement therapy use (HRT, OR = 2.6, 95% CI = 1.6-4.4 for 4(th) quartile versus lowest quartile). The multiplicative interaction terms were statistically significant only for physical activity and HRT. The positive association between plasma protein carbonyl levels and breast cancer risk was also observed when the analysis was restricted to women who had not received chemotherapy or radiation therapy prior to blood collection. Among controls, oxidized protein levels significantly increased with cigarette smoking and higher fruit and vegetable consumption, and decreased with alcohol consumption >30 grams per day. Women with higher levels of plasma protein carbonyl and urinary 15F(2t)-isoprostane had an 80% increase in breast cancer risk (OR = 1.8, 95% CI = 1.2-2.6) compared to women with levels below the median for both markers of oxidative stress. In summary, our results suggest that increased plasma protein carbonyl levels may be associated with breast cancer risk.

  8. Optimized biotin-hydrazide enrichment and mass spectrometry analysis of peptide carbonyls

    DEFF Research Database (Denmark)

    Havelund, Jesper F.; Wojdyla, K; Jensen, O. N.;

    Irreversible cell damage through protein carbonylation is the result of reaction with reactive oxygen species (ROS) and has been coupled to many diseases. The precise molecular consequences of protein carbonylation, however, are still not clear. The localization of the carbonylated amino acid is ...

  9. A specific gas chromatographic detector for carbonyl compounds, based on polarography.

    Science.gov (United States)

    Fleet, B; Risby, T H

    1969-07-01

    The evaluation of a specific gas Chromatographie detector for carbonyl compounds is described. This is based on the polarographic reduction of the Girard T hydrazone derivative which is formed when the carbonyl compound is absorbed in a buffered supporting electrolyte containing the carbonyl reagent. The detector was used to monitor the separation of a homologous series of alkanals.

  10. Low pressure carbonylation of benzyl chloride = Die carbonylierung von benzylchlorid bei niedrigen drücken

    NARCIS (Netherlands)

    Luggenhorst, H.J.; Westerterp, K.R.

    1986-01-01

    For carbonylations, metal carbonyls, particularly cobalt and iron carbonyls, are often used as catalysts. These reactions take place under rather drastic reaction conditions, e.g. 200–300 °C and 60–100 MPa. In some patents it is stated that similar reactions using the same catalysts can also be carr

  11. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke.

    Science.gov (United States)

    Pang, Xiaobing; Lewis, Alastair C

    2011-11-01

    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 μg cigarette(-1) (μg cig(-1)) and the particulate carbonyl emissions varied in the range of 23-127 μg cig(-1). Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 μg cig(-1) gaseous and 141 μg cig(-1) particulate carbonyls, which is 2-4 times greater than the cigarettes.

  12. Carbonyl Alkyl Nitrates as Trace Constituents in Urban Air

    Science.gov (United States)

    Woidich, S.; Gruenert, A.; Ballschmiter, K.

    2003-04-01

    Organic nitrates, esters of nitric acid, significantly contribute to the entire pool of odd nitrogen (NOY) in the atmosphere. Organic nitrates are formed in NO rich air by degradation of alkanes and alkenes initiated by OH and NO3 radicals during daytime and nighttime, respectively. Bifunctional organonitrates like the alkyl dinitrates and hydroxy alkyl nitrates are formed primarily from alkenes. The two main sources for Alkenes are traffic emissions and naturally occurring terpenes. So far a broad spectrum of alkyl dinitrates and hydroxy alkyl nitrates including six different isoprene nitrates has been identified in urban and marine air (1-3). We report here for the first time about the group of C4 C7 carbonyl alkyl nitrates as trace constituents in urban air collected on the campus of the University of Ulm Germany, and in the downtown area of Salt Lake City, Utah. Air sampling was done by high volume sampling (flow rate 25 m3/h) using a layer of 100 g silica gel (particle diameter 0.2 - 0.5 mm) as adsorbent. The organic nitrates were eluted from the silica gel by pentane/acetone (4:1, w/w) and the extract was concentrated to a volume of 500 µL for a group separation using normal phase HPLC. Final analysis was performed by high resolution capillary gas chromatography with electron capture detection as well as by mass selective detection in the (CH4)NCI mode using NO2- = m/e 46 as the indicator mass. The carbonyl alkyl nitrates were identified by self synthesized reference standards . So far we have identified eight non-branched a-carbonyl alkyl nitrates (vicinal carbonyl alkyl nitrates), two b-carbonyl alkyl nitrates and one g-carbonyl alkyl nitrate with carbon chains ranging from C4 to C7. The mixing ratios are between 0.05 and 0.30 ppt(v) for daytime samples and are two to three times higher for samples taken at night. (1) M. Schneider, O. Luxenhofer, Angela Deißler, K. Ballschmiter: 2C1-C15 Alkyl Nitrates, Benzyl Nitrate, and Bifunctional Nitrates

  13. Phenolic carbonyls undergo rapid aqueous photodegradation to form low-volatility, light-absorbing products

    Science.gov (United States)

    Smith, Jeremy D.; Kinney, Haley; Anastasio, Cort

    2016-02-01

    We investigated the aqueous photochemistry of six phenolic carbonyls - vanillin, acetovanillone, guaiacyl acetone, syringaldehyde, acetosyringone, and coniferyl aldehyde - that are emitted from wood combustion. The phenolic carbonyls absorb significant amounts of solar radiation and decay rapidly via direct photodegradation, with lifetimes (τ) of 13-140 min under Davis, CA winter solstice sunlight at midday (solar zenith angle = 62°). The one exception is guaiacyl acetone, where the carbonyl group is not directly connected to the aromatic ring: This species absorbs very little sunlight and undergoes direct photodegradation very slowly (τ > 103 min). We also found that the triplet excited states (3C*) of the phenolic carbonyls rapidly oxidize syringol (a methoxyphenol without a carbonyl group), on timescales of 1-5 h for solutions containing 5 μM phenolic carbonyl. The direct photodegradation of the phenolic carbonyls, and the oxidation of syringol by 3C*, both efficiently produce low volatility products, with SOA mass yields ranging from 80 to 140%. Contrary to most aliphatic carbonyls, under typical fog conditions we find that the primary sink for the aromatic phenolic carbonyls is direct photodegradation in the aqueous phase. In areas of significant wood combustion, phenolic carbonyls appear to be small but significant sources of aqueous SOA: over the course of a few hours, nearly all of the phenolic carbonyls will be converted to SOA via direct photodegradation, enhancing the POA mass from wood combustion by approximately 3-5%.

  14. Metal Carbonyl-Hydrosilane Reactions and Hydrosilation Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, A. R.

    2001-04-14

    Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a siloxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Three relevant catalytic reactions are shown. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(C0){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(I) precatalysts.

  15. Nuclear chemistry. Synthesis and detection of a seaborgium carbonyl complex.

    Science.gov (United States)

    Even, J; Yakushev, A; Düllmann, Ch E; Haba, H; Asai, M; Sato, T K; Brand, H; Di Nitto, A; Eichler, R; Fan, F L; Hartmann, W; Huang, M; Jäger, E; Kaji, D; Kanaya, J; Kaneya, Y; Khuyagbaatar, J; Kindler, B; Kratz, J V; Krier, J; Kudou, Y; Kurz, N; Lommel, B; Miyashita, S; Morimoto, K; Morita, K; Murakami, M; Nagame, Y; Nitsche, H; Ooe, K; Qin, Z; Schädel, M; Steiner, J; Sumita, T; Takeyama, M; Tanaka, K; Toyoshima, A; Tsukada, K; Türler, A; Usoltsev, I; Wakabayashi, Y; Wang, Y; Wiehl, N; Yamaki, S

    2014-09-19

    Experimental investigations of transactinoide elements provide benchmark results for chemical theory and probe the predictive power of trends in the periodic table. So far, in gas-phase chemical reactions, simple inorganic compounds with the transactinoide in its highest oxidation state have been synthesized. Single-atom production rates, short half-lives, and harsh experimental conditions limited the number of experimentally accessible compounds. We applied a gas-phase carbonylation technique previously tested on short-lived molybdenum (Mo) and tungsten (W) isotopes to the preparation of a carbonyl complex of seaborgium, the 106th element. The volatile seaborgium complex showed the same volatility and reactivity with a silicon dioxide surface as those of the hexacarbonyl complexes of the lighter homologs Mo and W. Comparison of the product's adsorption enthalpy with theoretical predictions and data for the lighter congeners supported a Sg(CO)6 formulation.

  16. Emissions of Toxic Carbonyls in an Electronic Cigarette

    Directory of Open Access Journals (Sweden)

    Guthery William

    2016-01-01

    Full Text Available Electronic cigarettes (e-cigs provide a smoke-free alternative for inhalation of nicotine without the vast array of toxic and carcinogenic combustion products produced by tobacco smoke. Elevated levels of toxic carbonyls may be generated during vaporisation; however, it is unclear whether that is indicative of a fault with the device or is due to the applied conditions of the test. A device, designed and built at this facility, was tested to determine the levels of selected toxic carbonyls. The reservoir was filled with approximately 960 mg of an e-liquid formulation containing 1.8% (w/v nicotine. Devices were puffed 200 times in blocks of 40 using a standardised regime consisting of a 55 mL puff volume; 3 s puff duration; 30 s puff interval; square wave puff profile. Confirmatory testing for nicotine and total aerosol delivery resulted in mean (n = 8 values of 10 mg (RSD 12.3% and 716 mg (RSD 11.2%, respectively. Emissions of toxic carbonyls were highly variable yet were between < 0.1% and 22.9% of expected levels from a Kentucky Reference Cigarette (K3R4F puffed 200 times under Health Canada Intense smoking conditions. It has been shown that a device built to a high specification with relatively consistent nicotine and aerosol delivery emits inconsistent levels of carbonyls. The exposure is greatly reduced when compared with lit tobacco products. However, it was observed that as the reservoirs neared depletion then emission levels were significantly higher

  17. Iron(III)-catalysed carbonyl-olefin metathesis.

    Science.gov (United States)

    Ludwig, Jacob R; Zimmerman, Paul M; Gianino, Joseph B; Schindler, Corinna S

    2016-04-27

    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

  18. Carbonylation of Ethene Catalysed by Pd(II-Phosphine Complexes

    Directory of Open Access Journals (Sweden)

    Gianni Cavinato

    2014-09-01

    Full Text Available This review deals with olefin carbonylation catalysed by Pd(II-phosphine complexes in protic solvents. In particular, the results obtained in the carbonylation with ethene are reviewed. After a short description of the basic concepts relevant to this catalysis, the review treats in greater details the influence of the bite angle, skeletal rigidity, electronic and steric bulk properties of the ligand on the formation of the products, which range from high molecular weight perfectly alternating polyketones to methyl propanoate. It is shown that the steric bulk plays a major role in directing the selectivity. Particular emphasis is given to the factors governing the very active and selective catalysis to methyl propanoate, including the mechanism of the catalytic cycles with diphosphine- and monophosphine-catalysts. A brief note on the synthesis of methyl propanoate using a “Lucite” type catalyst in ionic liquids is also illustrated. A chapter is dedicated to the carbonylation of olefins in aqueous reaction media. The nonalternating CO-ethene copolymerization is also treated.

  19. Iron(III)-catalysed carbonyl-olefin metathesis

    Science.gov (United States)

    Ludwig, Jacob R.; Zimmerman, Paul M.; Gianino, Joseph B.; Schindler, Corinna S.

    2016-05-01

    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

  20. Beads,Necklaces, Chains and Strings in Capping Carbonyl Clusters

    Directory of Open Access Journals (Sweden)

    Enos Masheija Kiremire

    2015-09-01

    Full Text Available The paper attempts to explain at length the close relationship between transition metal carbonyl clusters with main group clusters especially the boranes using the 14n and 4n rules. When the ‘shielding’ electrons are removed from a transition metal carbonyl cluster and becomes ‘naked’, it resembles a corresponding one in the main group elements. A an expanded table of osmium carbonyl clusters was constructed using the capping fragment Os(CO2(14n-2 and the fragment Os(CO3 (14n+0. The table reveals the fact that the known series such closo, nido and arachno are part and parcel of a wide range of series especially the capping series 14n+q, where q takes up negative multiple integers of two including 0 such as such = 0, -2,-4, -6, and so on. The linkage between capping series in transition metal carbonyl clusters has also been identified. Apart from the capping series generated in the table, there is another type of series where the skeletal cluster elements remained the same but the number of carbonyl ligands successively decreased. These types of series are referred to as stripping series. Mapping generating functions were also derived which produces any cluster formula or series required. Also the table shows that many clusters form utilizing some of its atoms as closo nucleus around which the larger ones are built and thus forming clusters within larger clusters. The table may be used to categorize a given cluster formula that falls within its range. Otherwise, using the 14n rule or 4n rule can be used for cluster classification. Furthermore, the table indicated that atoms, fragments and molecules can be classified into series. Through this approach of using series, Hoffmann’s important isolobal relationship of chemical species can splendidly be explained.Using the 14n rule and 4n rules creates a framework under which chemical species such as atoms, fragments, molecules and ions some of which may appear unrelated from main group

  1. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Xiaobing, E-mail: pangxbyuanj@gmail.com [Department of Chemistry, University of York, Heslington, York, YO10 5DD (United Kingdom); Lewis, Alastair C., E-mail: ally.lewis@york.ac.uk [National Centre for Atmospheric Science, University of York, Heslington, York, YO10 5DD (United Kingdom)

    2011-11-01

    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 {mu}g cigarette{sup -1} ({mu}g cig{sup -1}) and the particulate carbonyl emissions varied in the range of 23-127 {mu}g cig{sup -1}. Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 {mu}g cig{sup -1} gaseous and 141 {mu}g cig{sup -1} particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: {yields} Carbonyl

  2. Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method

    Energy Technology Data Exchange (ETDEWEB)

    Black, Stuart; Ferrell, Jack R.

    2017-01-01

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. Specifically, carbonyls cause an increase in viscosity (often referred to as 'aging') during storage of bio-oils. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Additionally, carbonyls are also responsible for coke formation in bio-oil upgrading processes. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here, we present a modification of the traditional carbonyl oximation procedures that results in less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. While traditional carbonyl oximation methods occur at room temperature, the Faix method presented here occurs at an elevated temperature of 80 degrees C.

  3. [Chemical Characteristics and Sources of Atmospheric Carbonyls During the 2014 Beijing APEC].

    Science.gov (United States)

    He, Xiao-lang; Tan, Ji-hua; Guo, Song-jun; Ma, Yong-liang; He, Ke-bin

    2016-03-15

    Pollution characteristic and variation trend of atmospheric carbonyls were investigated in November during the 2014 Beijing APEC. Formaldehyde, acetaldehyde and acetone were the dominant carbonyls, accounting for 82.66% of total carbonyls, and especially, formaldehyde accounted for 40.12% of total carbonyls. Atmospheric concentrations of total carbonyls decreased by around 64.10% after the clean air policy was carried out during the Beijing APEC, and the variation trend of carbonyls showed a similar pattern to those of other pollutants like PM₂.₅ during the APEC. Strong correlations (R² of 0.67-0.98) were observed among formaldehyde, acetaldehyde, acetone and total carbonyls during and after the APEC, indicating that they had similar sources; however, poor correlations (R² of -0.11-0.42 and 0.16-0.94, respectively) were observed before the APEC, implying different emission sources for ambient carbonyls. The calculated ratios of C1/C2, C2/C3 and OC/EC indicated that both vehicles and coal emissions were responsible for atmospheric carbonyls before the APEC, and emissions from coal burning were the major contributor to atmospheric carbonyls during and after the APEC, especially after the APEC.

  4. Indoor carbonyl compounds in an academic building in Beijing, China: concentrations and influencing factors

    Institute of Scientific and Technical Information of China (English)

    Chuanjia JIANG; Pengyi ZHANG

    2012-01-01

    Carbonyl compounds in indoor air are of great concern for their adverse health effects. Between February and May, 2009, concentrations of 13 carbonyl compounds were measured in an academic building in Beijing, China. Total concentration of the detected carbonyls ranged from 20.7 to 189.1 I.tg.m3, and among them acetone and formaldehyde were the most abundant, with mean concentrations of 26.4 and 22.6gg.m-3, respectively. Average indoor concentrations of other carbonyls were below I 0 gg. m~3. Principal component analysis identified a combined effect of common indoor carbonyl sources and ventilation on indoor carbonyl levels. Diurnal variations of the carbonyl compounds were investigated in one office room, and carbonyl concentrations tended to be lower in the daytime than at night, due to enhanced ventilation. Average concentrations of carbonyl compounds in the office room were generally higher in early May than in late February, indicating the influence of temperature. Carbo- nyl source emission rates from both the room and human occupants were estimated during two lectures, based on one-compartment mass balance model. The influence of human occupants on indoor carbonyl concentrations varies with environmental conditions, and may become signifi- cant in the case of a large human occupancy.

  5. Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method.

    Science.gov (United States)

    Black, Stuart; Ferrell, Jack R

    2017-02-07

    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. Specifically, carbonyls cause an increase in viscosity (often referred to as 'aging') during storage of bio-oils. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Additionally, carbonyls are also responsible for coke formation in bio-oil upgrading processes. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here, we present a modification of the traditional carbonyl oximation procedures that results in less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. While traditional carbonyl oximation methods occur at room temperature, the Faix method presented here occurs at an elevated temperature of 80 °C.

  6. Determination of Carbonyl Compounds in Cigarette Mainstream Smoke. The CORESTA 2010 Collaborative Study and Recommended Method

    Directory of Open Access Journals (Sweden)

    Intorp M

    2014-12-01

    Full Text Available A recommended method has been developed and published by CORESTA, applicable to the quantification of selected carbonyl compounds (acetaldehyde, formaldehyde, acetone, acrolein, methyl ethyl ketone, crotonaldehyde, propionaldehyde and butyraldehyde in cigarette mainstream smoke. The method involved smoke collection in impinger traps, derivatisation of carbonyls with 2,4-dinitrophenylhydrazine (DNPH, separation of carbonyl hydrazones by reversed phase high performance liquid chromatography and detection by ultra violet or diode array.

  7. Two-dimensional gel electrophoretic detection of protein carbonyls derivatized with biotin-hydrazide.

    Science.gov (United States)

    Wu, Jinzi; Luo, Xiaoting; Jing, Siqun; Yan, Liang-Jun

    2016-04-15

    Protein carbonyls are protein oxidation products that are often used to measure the magnitude of protein oxidative damage induced by reactive oxygen or reactive nitrogen species. Protein carbonyls have been found to be elevated during aging and in age-related diseases such as stroke, diabetes, and neurodegenerative diseases. In the present article, we provide detailed protocols for detection of mitochondrial protein carbonyls labeled with biotin-hydrazide followed by 2-dimensional isoelectric focusing (IEF)/SDS-PAGE and Western blotting probed with horse-radish peroxidase-conjugated streptavidin. The presented procedures can also be modified for detection of carbonylation of non-mitochondrial proteins.

  8. A biotin enrichment strategy identifies novel carbonylated amino acids in proteins from human plasma

    DEFF Research Database (Denmark)

    Havelund, Jesper F.; Wojdyla, Katarzyna; Davies, Michael J.

    2017-01-01

    Protein carbonylation is an irreversible protein oxidation correlated with oxidative stress, various diseases and ageing. Here we describe a peptide-centric approach for identification and characterisation of up to 14 different types of carbonylated amino acids in proteins. The modified residues...... in vitro metal ion-catalysed oxidation. Furthermore, we assigned 133 carbonylated sites in 36 proteins in native human plasma protein samples. The optimised workflow enabled detection of 10 hitherto undetected types of carbonylated amino acids in proteins: aldehyde and ketone modifications of leucine...

  9. Nano-Aluminum Powder Mediated Allylation of Carbonyl Compounds in Aqueous Media

    Institute of Scientific and Technical Information of China (English)

    YUAN Shi-Zhen; LIU Jin

    2008-01-01

    A new and effective Barbier-Grignard allylation of aldehydes or ketones has been carried out with nano-aluminum powder in aqueous 0.1 mol·L-1 NH4Cl (aq.) under an atmosphere of nitrogen. Aromatic carbonyl compounds gave homoallylic alcohols in good yields. The effectiveness of reaction was strongly influenced by the steric environment surrounding the carbonyl group. Aliphatic carbonyl compounds proceeded in low yields. The dominant stereoisomer was an erythro-isomer when an ortho-hydroxyl carbonyl compound was reacted under such a reaction condition.

  10. Reactive Carbonyl Species In Vivo: Generation and Dual Biological Effects

    Directory of Open Access Journals (Sweden)

    Halyna M. Semchyshyn

    2014-01-01

    Full Text Available Reactive carbonyls are widespread species in living organisms and mainly known for their damaging effects. The most abundant reactive carbonyl species (RCS are derived from oxidation of carbohydrates, lipids, and amino acids. Chemical modification of proteins, nucleic acids, and aminophospholipids by RCS results in cytotoxicity and mutagenicity. In addition to their direct toxicity, modification of biomolecules by RCS gives rise to a multitude of adducts and cross links that are increasingly implicated in aging and pathology of a wide range of human diseases. Understanding of the relationship between metabolism of RCS and the development of pathological disorders and diseases may help to develop effective approaches to prevent a number of disorders and diseases. On the other hand, constant persistence of RCS in cells suggests that they perform some useful role in living organisms. The most beneficial effects of RCS are their establishment as regulators of cell signal transduction and gene expression. Since RCS can modulate different biological processes, new tools are required to decipher the precise mechanisms underlying dual effects of RCS.

  11. Glutathione Adduct Patterns of Michael-Acceptor Carbonyls.

    Science.gov (United States)

    Slawik, Christian; Rickmeyer, Christiane; Brehm, Martin; Böhme, Alexander; Schüürmann, Gerrit

    2017-02-22

    Glutathione (GSH) has so far been considered to facilitate detoxification of soft organic electrophiles through covalent binding at its cysteine (Cys) thiol group, followed by stepwise catalyzed degradation and eventual elimination along the mercapturic acid pathway. Here we show that in contrast to expectation from HSAB theory, Michael-acceptor ketones, aldehydes and esters may form also single, double and triple adducts with GSH involving β-carbon attack at the much harder N-terminus of the γ-glutamyl (Glu) unit of GSH. In particular, formation of the GSH-N single adduct contradicts the traditional view that S alkylation always forms the initial reaction of GSH with Michael-acceptor carbonyls. To this end, chemoassay analyses of the adduct formation of GSH with nine α,β-unsaturated carbonyls employing high performance liquid chromatography and tandem mass spectrometry have been performed. Besides enriching the GSH adductome and potential biomarker applications, electrophilic N-terminus functio-nalization is likely to impair GSH homeostasis substantially through blocking the γ-glutamyl transferase catalysis of the first breakdown step of modified GSH, and thus its timely reconstitution. The discussion includes a comparison with cyclic adducts of GSH and furan metabolites as reported in literature, and quantum chemically calculated thermodynamics of hard-hard, hard-soft and soft-soft adducts.

  12. IRC analysis of methanol carbonylation reaction catalyzed by rhodium complex

    Institute of Scientific and Technical Information of China (English)

    HAO Maorong; FENG Wenlin; JI Yongqiang; LEI Ming

    2004-01-01

    In the reaction cycle for methanol carbonylation catalyzed by Rh complex, the structure geometries of the reactant, intermediates, transition states and product of each elemental reaction have been studied by using the energy gradient method at HF/LANL2DZ level, and the changes of their potential profiles have also been calculated. Through IRC analyses of the transition states for each elemental reaction, it is confirmed that the various structure geometries obtained are stationary points on the cycle reaction pathway of methanol carbonylation catalyzed by Rh complex, and the changes are given in energies and structure geometries of the reactant molecules along the reaction pathway of lowest energy. It has been proposed that the geometrical conversions of intermediates play an important role during the cycle reaction. Through analyses of structure geometries, it has been suggested that, in addition to cis- and trans- structure exchange linkage of catalysis reactive species, the two pathways, cis- and trans-cata- lyzed cycle reactions, can also be linked through geometrical conversion of intermediates, of which the activation energy is 49.79 kJ/mol. Moreover, the reductive elimination elemental reaction may be neither cis-cycle nor trans- one, showing that the cycle reaction can be achieved through various pathways. However different the pathway, the oxidative addition elemental reaction of CH3I is the rate-controlling step.

  13. Transition-metal-catalyzed carbonylation reactions of olefins and alkynes: a personal account.

    Science.gov (United States)

    Wu, Xiao-Feng; Fang, Xianjie; Wu, Lipeng; Jackstell, Ralf; Neumann, Helfried; Beller, Matthias

    2014-04-15

    Carbon monoxide was discovered and identified in the 18th century. Since the first applications in industry 80 years ago, academic and industrial laboratories have broadly explored CO's use in chemical reactions. Today organic chemists routinely employ CO in organic chemistry to synthesize all kinds of carbonyl compounds. Despite all these achievements and a century of carbonylation catalysis, many important research questions and challenges remain. Notably, apart from academic developments, industry applies carbonylation reactions with CO on bulk scale. In fact, today the largest applications of homogeneous catalysis (regarding scale) are carbonylation reactions, especially hydroformylations. In addition, the vast majority of acetic acid is produced via carbonylation of methanol (Monsanto or Cativa process). The carbonylation of olefins/alkynes with nucleophiles, such as alcohols and amines, represent another important type of such reactions. In this Account, we discuss our work on various carbonylations of unsaturated compounds and related reactions. Rhodium-catalyzed isomerization and hydroformylation reactions of internal olefins provide straightforward access to higher value aldehydes. Catalytic hydroaminomethylations offer an ideal way to synthesize substituted amines and even heterocycles directly. More recently, our group has also developed so-called alternative metal catalysts based on iridium, ruthenium, and iron. What about the future of carbonylation reactions? CO is already one of the most versatile C1 building blocks for organic synthesis and is widely used in industry. However, because of CO's high toxicity and gaseous nature, organic chemists are often reluctant to apply carbonylations more frequently. In addition, new regulations have recently made the transportation of carbon monoxide more difficult. Hence, researchers will need to develop and more frequently use practical and benign CO-generating reagents. Apart from formates, alcohols, and metal

  14. A step-by-step protocol for assaying protein carbonylation in biological samples.

    Science.gov (United States)

    Colombo, Graziano; Clerici, Marco; Garavaglia, Maria Elisa; Giustarini, Daniela; Rossi, Ranieri; Milzani, Aldo; Dalle-Donne, Isabella

    2016-04-15

    Protein carbonylation represents the most frequent and usually irreversible oxidative modification affecting proteins. This modification is chemically stable and this feature is particularly important for storage and detection of carbonylated proteins. Many biochemical and analytical methods have been developed during the last thirty years to assay protein carbonylation. The most successful method consists on protein carbonyl (PCO) derivatization with 2,4-dinitrophenylhydrazine (DNPH) and consequent spectrophotometric assay. This assay allows a global quantification of PCO content due to the ability of DNPH to react with carbonyl giving rise to an adduct able to absorb at 366 nm. Similar approaches were also developed employing chromatographic separation, in particular HPLC, and parallel detection of absorbing adducts. Subsequently, immunological techniques, such as Western immunoblot or ELISA, have been developed leading to an increase of sensitivity in protein carbonylation detection. Currently, they are widely employed to evaluate change in total protein carbonylation and eventually to highlight the specific proteins undergoing selective oxidation. In the last decade, many mass spectrometry (MS) approaches have been developed for the identification of the carbonylated proteins and the relative amino acid residues modified to carbonyl derivatives. Although these MS methods are much more focused and detailed due to their ability to identify the amino acid residues undergoing carbonylation, they still require too expensive equipments and, therefore, are limited in distribution. In this protocol paper, we summarise and comment on the most diffuse protocols that a standard laboratory can employ to assess protein carbonylation; in particular, we describe step-by-step the different protocols, adding suggestions coming from our on-bench experience.

  15. Influences of characteristic meteorological conditions on atmospheric carbonyls in Beijing, China

    Science.gov (United States)

    Pang, Xiaobing; Mu, Yujing; Lee, Xinqing; Zhang, Yujie; Xu, Zhu

    2009-08-01

    Atmospheric pollutants are controlled not only by their production rates but also by meteorological conditions. The influences of dust storm, sauna weather (haze with high temperature and high humidity), wet precipitation and wind speed on atmospheric carbonyls in Beijing were investigated. During a severe dust episode (April 17, 2006), the mixing ratios of carbonyls were significantly elevated to 13-27 ppbV from 7 to 13 ppbV in the previous non-dust days (April 15 and 16) with the increasing extents of 38-154%. The accumulating effect and the lower photolysis rate in the dust day may be responsible for the increases of carbonyls' levels. Additionally, the contribution from heterogeneous reactions occurring on dust particles to formaldehyde and acetaldehyde cannot be ruled out. During the period of typical sauna weather, the concentrations of atmospheric carbonyls increased to 18-60 ppbV from 10 to 17 ppbV before the sauna days. The air mass over Beijing during the sauna days was controlled by a subtropical anticyclone and the boundary layer became quite stable, which was beneficial to the rapid accumulation of air pollutants including carbonyls. Wet precipitation was found to be an effective removal process to the atmospheric carbonyls. After one-hour of rain in summer, the total concentrations of atmospheric carbonyls decreased to less than half of that before the rainfall. The similar temporal varying patterns of carbonyls and inorganic ions in rainwater indicated that carbonyls were mainly washed out from the atmosphere into rainwater as inorganic ions were. Strong wind could evidently dilute atmospheric carbonyls and a negative correlation was found between wind speeds and the concentrations of carbonyls in spring in Beijing.

  16. Structural characteristics of green tea catechins for formation of protein carbonyl in human serum albumin.

    Science.gov (United States)

    Ishii, Takeshi; Mori, Taiki; Ichikawa, Tatsuya; Kaku, Maiko; Kusaka, Koji; Uekusa, Yoshinori; Akagawa, Mitsugu; Aihara, Yoshiyuki; Furuta, Takumi; Wakimoto, Toshiyuki; Kan, Toshiyuki; Nakayama, Tsutomu

    2010-07-15

    Catechins are polyphenolic antioxidants found in green tea leaves. Recent studies have reported that various polyphenolic compounds, including catechins, cause protein carbonyl formation in proteins via their pro-oxidant actions. In this study, we evaluate the formation of protein carbonyl in human serum albumin (HSA) by tea catechins and investigate the relationship between catechin chemical structure and its pro-oxidant property. To assess the formation of protein carbonyl in HSA, HSA was incubated with four individual catechins under physiological conditions to generate biotin-LC-hydrazide labeled protein carbonyls. Comparison of catechins using Western blotting revealed that the formation of protein carbonyl in HSA was higher for pyrogallol-type catechins than the corresponding catechol-type catechins. In addition, the formation of protein carbonyl was also found to be higher for the catechins having a galloyl group than the corresponding catechins lacking a galloyl group. The importance of the pyrogallol structural motif in the B-ring and the galloyl group was confirmed using methylated catechins and phenolic acids. These results indicate that the most important structural element contributing to the formation of protein carbonyl in HSA by tea catechins is the pyrogallol structural motif in the B-ring, followed by the galloyl group. The oxidation stability and binding affinity of tea catechins with proteins are responsible for the formation of protein carbonyl, and consequently the difference in these properties of each catechin may contribute to the magnitude of their biological activities.

  17. Iron(III)-Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Saá, Carlos

    2016-09-01

    Recent developments in catalytic carbonyl-olefin metathesis are summarized in this Highlight. Schindler and co-workers have reported that the environmentally benign FeCl3 catalyst promotes ring-closing carbonyl-olefin metathesis (RCCOM) in high yield under very mild conditions.

  18. Preparation and microwave shielding property of silver-coated carbonyl iron powder

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Xiao Guo, E-mail: xgcao@gdut.edu.cn [School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, Guangdong (China); Ren, Hao [Guangzhou Research Institute of O-M-E Technology, Guangzhou 510006, Guangdong (China); Zhang, Hai Yan [School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, Guangdong (China)

    2015-05-15

    Highlights: • The silver-coated carbonyl iron powder is prepared by the electroless plating process. • The silver-coated carbonyl iron powder is a new kind of conductive filler. • The reflection and absorption dominate the shielding mechanism of the prepared powder. • Increasing the thickness of electroconductive adhesive will increase the SE. - Abstract: Electroless silver coating of carbonyl iron powder is demonstrated in the present investigation. The carbonyl iron powders are characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction analysis (XRD) before and after the coating process. The relatively uniform and continuous silver coating is obtained under the given coating conditions. In this paper, the electromagnetic interference (EMI) shielding mechanism of the silver-coated carbonyl iron powder is suggested. The reflection of silver coating and absorption of carbonyl iron powder dominate the shielding mechanism of the silver-coated carbonyl iron powder. The silver-coated carbonyl iron powders are used as conductive filler in electroconductive adhesive for electromagnetic interference shielding applications. The effect of the thickness of electroconductive adhesive on the shielding effectiveness (SE) is investigated. The results indicate that the SE increases obviously with the increase of the thickness of electroconductive adhesive. The SE of the electroconductive adhesive with 0.35 mm thickness is above 38 dB across the tested frequency range.

  19. Impact of HVAC filter on indoor air quality in terms of ozone removal and carbonyls generation

    Science.gov (United States)

    Lin, Chi-Chi; Chen, Hsuan-Yu

    2014-06-01

    This study aims at detecting ozone removal rates and corresponding carbonyls generated by ozone reaction with HVAC filters from various building, i.e., shopping mall, school, and office building. Studies were conducted in a small-scale environmental chamber. By examining dust properties including organic carbon proportion and specific surface area of dusts adsorbed on filters along with ozone removal rates and carbonyls generation rate, the relationship among dust properties, ozone removal rates, and carbonyls generation was identified. The results indicate a well-defined positive correlation between ozone removal efficiency and carbonyls generation on filters, as well as a positive correlation among the mass of organic carbon on filters, ozone removal efficiency and carbonyls generations.

  20. Protein carbonylation and metal-catalyzed protein oxidation in a cellular perspective

    DEFF Research Database (Denmark)

    Møller, Ian Max; Rogowska-Wrzesinska, Adelina; Rao, R S P

    2011-01-01

    Proteins can become oxidatively modified in many different ways, either by direct oxidation of amino acid side chains and protein backbone or indirectly by conjugation with oxidation products of polyunsaturated fatty acids and carbohydrates. While reversible oxidative modifications are thought...... to be relevant in physiological processes, irreversible oxidative modifications are known to contribute to cellular damage and disease. The most well-studied irreversible protein oxidation is carbonylation. In this work we first examine how protein carbonylation occurs via metal-catalyzed oxidation (MCO) in vivo...... and in vitro with an emphasis on cellular metal ion homeostasis and metal binding. We then review proteomic methods currently used for identifying carbonylated proteins and their sites of modification. Finally, we discuss the identified carbonylated proteins and the pattern of carbonylation sites in relation...

  1. Carbonyl mediated conductance through metal bound peptides: a computational study

    Science.gov (United States)

    Perrine, Trilisa M.; Dunietz, Barry D.

    2007-10-01

    Large increases in the conductance of peptides upon binding to metal ions have recently been reported experimentally. The mechanism of the conductance switching is examined computationally. It is suggested that oxidation of the metal ion occurs after binding to the peptide. This is caused by the bias potential placed across the metal-peptide complex. A combination of configurational changes, metal ion involvement and interactions between carbonyl group oxygen atoms and the gold leads are all shown to be necessary for the large improvement in the conductance seen experimentally. Differences in the molecular orbitals of the nickel and copper complexes are noted and serve to explain the variation of the improvement in conductance upon binding to either a nickel or copper ion.

  2. Uptake and conversion of carbonyl sulfide in a lawn soil

    Science.gov (United States)

    Liu, Junfeng; Mu, Yujing; Geng, Chunmei; Yu, Yunbo; He, Hong; Zhang, Yuanhang

    Carbonyl sulfide (COS) exchange fluxes between a lawn soil and the atmosphere as well as influencing factors (temperature and water content of soil) were investigated using a static cuvette. The optimal soil temperature and water content for COS consumption were about 298 K and 12.5%, respectively. The converting products of the consumed COS in the lawn soil were researched using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The peaks of gas-phase products of CO2 and surface HCO3-, HS-, SO32-, HSO3-, and SO42- species were observed. The possible mechanism of COS conversion in the lawn soil was discussed. The conversion rates of consumed COS into water-soluble sulfate in the lawn soil were studied by ion chromatography (IC). The experimental results show that about 50% sulfur from the soil consumed COS was eventually converted into water-soluble sulfate.

  3. Direct Vapor Phase Carbonylation of Methanol over NiCl2/C Catalyst

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    @@ Introduction The carbonylation of alcohols via homogenous catalysis is important in manufacturing acetic acid and higher carboxylic acids and their esters[1,2]. The main route to produce acetic acid is to make methanol carbonylated by means of the Monsanto and BP process in which a homogeneous rhodium catalyst is used. Although the homogeneous carbonylation of methanol is a highly selective process, it is affected by the disadvantages associated with a highly corrosive reaction medium due to the use of methyl iodide as the promoter, and the difficulty of the product separation[3]. The use of a heterogeneous catalyst seems very interesting and attractive to us[4], especially the direct vapor phase carbonylation of methanol without a halide promoter is of considerable importance and is strong incentive economically. There has, however, been very little success in finding either heterogeneous or homogeneous catalysts that can catalyze the reaction effectively without the addition of a promoter[5,6]. According to the known carbonylation mechanism[7,8], the methyl iodide directly carbonylates with CO to from MeCOI which interacts with methanol(MeOH) to produce methyl acetate(MeCOOMe) and HI, and then MeOH reacts with HI to from CH3I. In fact, this carbonylation reaction is the indirect catalytic carbonylation of methanol[9]. In this work, a novel catalyst for the direct vapor phase carbonylation of methanol without the addition of any halide in the feed as a promoter was investigated. Compared to the known liquid phase methanol carbonylation process, some advantages of this vapor phase reaction are as follows:

  4. Anti-Amoebic Properties of Carbonyl Thiourea Derivatives

    Directory of Open Access Journals (Sweden)

    Maizatul Akma Ibrahim

    2014-04-01

    Full Text Available Thiourea derivatives display a broad spectrum of applications in chemistry, various industries, medicines and various other fields. Recently, different thiourea derivatives have been synthesized and explored for their anti-microbial properties. In this study, four carbonyl thiourea derivatives were synthesized and characterized, and then further tested for their anti-amoebic properties on two potential pathogenic species of Acanthamoeba, namely A. castellanii (CCAP 1501/2A and A. polyphaga (CCAP 1501/3A. The results indicate that these newly-synthesized thiourea derivatives are active against both Acanthamoeba species. The IC50 values obtained were in the range of 2.39–8.77 µg·mL‑1 (9.47–30.46 µM for A. castellanii and 3.74–9.30 µg·mL‑1 (14.84–31.91 µM for A. polyphaga. Observations on the amoeba morphology indicated that the compounds caused the reduction of the amoeba size, shortening of their acanthopodia structures, and gave no distinct vacuolar and nuclear structures in the amoeba cells. Meanwhile, fluorescence microscopic observation using acridine orange and propidium iodide (AOPI staining revealed that the synthesized compounds induced compromised-membrane in the amoeba cells. The results of this study proved that these new carbonyl thiourea derivatives, especially compounds M1 and M2 provide potent cytotoxic properties toward pathogenic Acanthamoeba to suggest that they can be developed as new anti-amoebic agents for the treatment of Acanthamoeba keratitis.

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

    Science.gov (United States)

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

    2017-01-01

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

  6. Electroless plating preparation and electromagnetic properties of Co-coated carbonyl iron particles/polyimide composite

    Science.gov (United States)

    Zhou, Yingying; Zhou, Wancheng; Li, Rong; Qing, Yuchang; Luo, Fa; Zhu, Dongmei

    2016-03-01

    To solve the serious electromagnetic interference problems at elevated temperature, one thin microwave-absorbing sheet employing Co-coated carbonyl iron particles and polyimide was prepared. The Co-coated carbonyl iron particles were successfully prepared using an electroless plating method. The microstructure, composition, phase and static magnetic properties of Co-coated carbonyl iron particles were characterized by combination of scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD) and vibrating sample magnetometer (VSM). The electromagnetic parameters of Co-coated carbonyl iron particles/polyimide composite were measured in the frequency range of 2-18 GHz, and the electromagnetic loss mechanism of the material-obtained was discussed. The microwave absorption properties of composites before and after heat treatment at 300 °C for 100 h were characterized in 2-18 GHz frequency range. It was established that composites based on Co-coated carbonyl iron demonstrate thermomagnetic stability, indicating that Co coating reduces the oxidation of carbonyl iron. Thus, Co-coated carbonyl iron particles/polyimide composites are useful in the design of microwave absorbers operating at temperatures up to 300 °C.

  7. Formation of Carbonyl and Carboxyl Groups on Cellulosic Pulps: Effect on Alkali Resistance

    Directory of Open Access Journals (Sweden)

    Jordan Perrin

    2014-10-01

    Full Text Available Ozone bleaching generates carbonyl groups on the cellulose polymer when applied to unbleached kraft pulps. This suggests that pulp fully bleached with a totally chlorine-free (TCF sequence may contain more oxidized groups than standard elemental chlorine-free (ECF bleached pulp. A fully bleached pulp was treated with sodium hypochlorite to form oxidized groups (mostly carbonyls on the pure carbohydrates, which were investigated during subsequent alkaline treatment. Carbonyl groups had a strong impact on color development during alkaline treatment. Among the carbonyls, the keto groups were the most active. This was confirmed by the behavior of carbohydrate model compounds that contained aldehyde, keto, and/or carboxyl groups when subjected to alkaline conditions. A subsequent hydrogen peroxide (P stage effectively decreased the carbonyl content, which reduced yellowing during alkaline treatment. However, the oxidized cellulose was severely depolymerized. The addition of magnesium sulfate (Mg into the P stage minimized depolymerization while maintaining some of the carbonyls in the carbohydrates. It is proposed that Mg cations can hinder alkaline β-elimination, possibly by forming a complex with the carbonyl groups.

  8. Paraquat exposure and Sod2 knockdown have dissimilar impacts on the Drosophila melanogaster carbonylated protein proteome.

    Science.gov (United States)

    Narayanasamy, Suresh K; Simpson, David C; Martin, Ian; Grotewiel, Mike; Gronert, Scott

    2014-11-01

    Exposure to Paraquat and RNA interference knockdown of mitochondrial superoxide dismutase (Sod2) are known to result in significant lifespan reduction, locomotor dysfunction, and mitochondrial degeneration in Drosophila melanogaster. Both perturbations increase the flux of the progenitor ROS, superoxide, but the molecular underpinnings of the resulting phenotypes are poorly understood. Improved understanding of such processes could lead to advances in the treatment of numerous age-related disorders. Superoxide toxicity can act through protein carbonylation. Analysis of carbonylated proteins is attractive since carbonyl groups are not present in the 20 canonical amino acids and are amenable to labeling and enrichment strategies. Here, carbonylated proteins were labeled with biotin hydrazide and enriched on streptavidin beads. On-bead digestion was used to release carbonylated protein peptides, with relative abundance ratios versus controls obtained using the iTRAQ MS-based proteomics approach. Western blotting and biotin quantitation assay approaches were also investigated. By both Western blotting and proteomics, Paraquat exposure, but not Sod2 knockdown, resulted in increased carbonylated protein relative abundance. For Paraquat exposure versus control, the median carbonylated protein relative abundance ratio (1.53) determined using MS-based proteomics was in good agreement with that obtained using a commercial biotin quantitation kit (1.36).

  9. Variation of ambient carbonyl levels in urban Beijing between 2005 and 2012

    Science.gov (United States)

    Chen, Wentai; Shao, Min; Wang, Ming; Lu, Sihua; Liu, Ying; Yuan, Bin; Yang, Yudong; Zeng, Limin; Chen, Zhongming; Chang, Chih-Chung; Zhang, Qian; Hu, Min

    2016-03-01

    Carbonyl compounds are important precursors of secondary air pollutants. With the rapid economic development and the implementation of stricter control measures in Beijing, the sources of carbonyls possibly changed. Based on measurement data obtained at an urban site in Beijing between 2005 and 2012, we investigated annual variations in carbonyl levels and sources during these years. In summer, formaldehyde and acetaldehyde levels decreased significantly at a rate of 9.1%/year and 7.2%/year, respectively, while acetone levels increased at a rate of 4.3%/year. In winter, formaldehyde levels increased and acetaldehyde levels decreased. We also investigated the factors driving the variation in carbonyls levels during summer by determination of emission ratios for carbonyls and their precursors, and calculation of photochemical formation of carbonyls. The relative declines for primary formaldehyde and acetaldehyde levels were larger than those for secondary formation. This is possibly due to the increasing usage of natural gas and liquefied petroleum gas which could result in the rise of carbonyl precursor emission ratios. The increase in acetone levels might be related to the rising solvent usage in Beijing during these years. The influences of these sources should be paid more attention in future research.

  10. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    Science.gov (United States)

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping

    2016-08-22

    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products.

  11. Visible Light-Induced Carbonylation Reactions with Organic Dyes as the Photosensitizers.

    Science.gov (United States)

    Peng, Jin-Bao; Qi, Xinxin; Wu, Xiao-Feng

    2016-09-01

    Dyes can CO do it: Organic dyes and pigments are usually applied in textile dyeing, which can be dated back to the Neolithic period. Interestingly, the possibility to use organic dyes as photoredox catalysts has also been noticed by organic chemists and applied in organic synthesis. Carbonylation reactions as a powerful procedure in carbonyl-containing compound preparation have also been studied. In this manuscript, the recent achievements in using organic dyes as visible-light sensitizers in carbonylation chemistry are summarized and discussed.

  12. Rovibrational Spectroscopy of Aluminum Carbonyl Clusters in Helium Nanodroplets

    Science.gov (United States)

    Liang, T.; Morrison, A. M.; Flynn, S. D.; Douberly, G. E.

    2011-06-01

    Helium nanodroplet isolation and a tunable quantum cascade laser are used to probe the fundamental CO stretch bands of Aluminum Carbonyl complexes, Al-(CO)N (n ≤ 5). The droplets are doped with single aluminum atoms via the resistive heating of an aluminum wetted tantalum wire. The downstream sequential pick-up of CO molecules leads to the rapid formation and cooling of Al-(CO)N clusters within the droplets. Near 1900 Cm-1, rotational fine structure is resolved in bands that are assigned to the CO stretch of a 2Π1/2 linear Al-CO species, and the asymmetric and symmetric CO stretch vibrations of a planar C2v Al-(CO)2 complex in a 2B1 electronic state. Bands corresponding to clusters with n ≥ 3 lack resolved rotational fine structure; nevertheless, the small frequency shifts from the n=2 bands indicate that these clusters consist of an Al-(CO)2 core with additional CO molecules attached via van-der-Waals interactions. A second n=2 band is observed near the CO stretch of Al-CO, indicating a local minimum on the n=2 potential consisting of an ``unreacted" Al-CO-(CO) cluster. The linewidth of this band is ˜0.5 cm-1, which is over 50 times broader than transitions within the Al-CO band. The additional broadening is consistent with a homogeneous mechanism corresponding to a rapid vibrational excitation induced reaction within the Al-CO-(CO) cluster to form the covalently bonded Al-(CO)2 complex. For the n=1,2 complexes, CCSD(T) calculations and Natural Bond Orbital (NBO) analyses are carried out to investigate the nature of the bonding in these complexes. The NBO calculations show that both π ``back" donation (from the occupied aluminum p-orbital into the π antibonding CO orbital) and σ donation (from CO into the empty aluminum p-orbitals) play a significant role in the bonding, analogous to transition metal carbonyl complexes. The large redshift of the CO stretch vibrations is consistent with this bonding analysis.

  13. Mechanism of heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    Science.gov (United States)

    Liu, Yongchun; He, Hong; Xu, Wenqing; Yu, Yunbo

    2007-05-24

    Heterogeneous reaction of carbonyl sulfide (OCS) on magnesium oxide (MgO) under ambient conditions was investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), quadrupole mass spectrometer (QMS), and density functional theory (DFT) calculations. It reveals that OCS can be catalytically hydrolyzed by surface hydroxyl on MgO to produce carbon dioxide (CO2) and hydrogen sulfide (H2S), and then H2S can be further catalytically oxidized by surface oxygen or gaseous oxygen on MgO to form sulfite (SO3(2-)) and sulfate (SO4(2-)). Hydrogen thiocarbonate (HSCO2-) was found to be the crucial intermediate. Surface hydrogen sulfide (HS), sulfur dioxide (SO2), and surface sulfite (SO3(2-)) were also found to be intermediates for the formation of sulfate. Furthermore, the surface hydroxyl contributes not only to the formation of HSCO2- but also to HSCO2- decomposition. On the basis of experimental results, the heterogeneous reaction mechanism of OCS on MgO was discussed.

  14. Thermal characterization of magnetically aligned carbonyl iron/agar composites.

    Science.gov (United States)

    Diaz-Bleis, D; Vales-Pinzón, C; Freile-Pelegrín, Y; Alvarado-Gil, J J

    2014-01-01

    Composites of magnetic particles into polymeric matrices have received increasing research interest due to their capacity to respond to external magnetic or electromagnetic fields. In this study, agar from Gelidium robustum has been chosen as natural biocompatible polymer to build the matrix of the magnetic carbonyl iron particles (CIP) for their uses in biomedical fields. Heat transfer behavior of the CIP-agar composites containing different concentrations (5, 10, 15, 20, 25 and 30% w/w) of magnetically aligned and non-aligned CIP in the agar matrix was studied using photothermal radiometry (PTR) in the back-propagation emission configuration. The morphology of the CIP-agar composites with aligned and non-aligned CIP under magnetic field was also evaluated by scanning electron microscopy (SEM). The results revealed a dominant effect of CIP concentration over the alignment patterns induced by the magnetic field, which agrees with the behavior of the thermal diffusivity and thermal conductivity. Agar served as a perfect matrix to be used with CIP, and CIP-agar composites magnetically aligned at 20% CIP concentration can be considered as promising 'smart' material for hyperthermia treatments in the biomedical field.

  15. Photodecomposition of Molybdenum andTungsten Carbonyl Complexes

    Directory of Open Access Journals (Sweden)

    Thamer A. Alwani

    2009-01-01

    Full Text Available The photodecomposition of four different colored organometallic molybdenum and tungsten carbonyl complexes, i.e. [Mo(CO52LA] (complex I, [(Mo(CO3(bipy2LB] (complex II, [(W(CO3(tmen2LB] (complex III and [Mo(CO2LC]2 (complex I V where LA 2-phenyl-1,3-indandionebis(2-methyl anilines, LB 2-phenyl-1,3-indandione bis (4-hydroxy anilines and LCbis (2-hydroxo-benzalydine benzidine ion have been performed at 365 nm in chloroform at 25 °C under oxygen atmosphere. The absorbance spectrum of these complexes has been recorded with the time of irradiation in order to examine the kinetics of photodecomposition. The rate of the photodecomposition process was investigated and the relative values of the rate constants of dissociation (Kd for the first-order reaction are tabulated. The apparent rate constant of photodecomposition was found to be (8.33-11.50 × 10-5 s-1.

  16. Tropical sources and sinks of carbonyl sulfide observed from space

    Science.gov (United States)

    Glatthor, Norbert; Höpfner, Michael; Baker, Ian T.; Berry, Joe; Campbell, Elliott; Kawa, Stephan R.; Krysztofiak, Gisele; Sinnhuber, Björn-Martin; Stiller, Gabriele; Stinecipher, Jim; von Clarmann, Thomas

    2016-04-01

    According to current budget estimations the seasonal variation of carbonyl sulfide (COS) is governed by oceanic release and vegetation uptake. Its assimilation by plants is assumed to be similar to the photosynthetic uptake of CO2 but, contrary to the latter process, to be irreversible. Therefore COS has been suggested as co-tracer of the carbon cycle. Observations of COS, however, are sparse, especially in tropical regions. We use the comprehensive data set of spaceborne measurements of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) to analyze its global distribution. Two major features are observed in the tropical upper troposphere around 250 hPa: enhanced amounts over the western Pacific and the Maritime Continent, peaking around 550 pptv in boreal summer, and a seasonally varying depletion of COS extending from tropical South America to Africa. The large-scale COS depletion, which in austral summer amounts up to -40 pptv as compared to the rest of the respective latitude band, has not been observed before and reveals the seasonality of COS uptake through tropical vegetation. The observations can only be reproduced by global models, when a large vegetation uptake and a corresponding increase in oceanic emissions as proposed in several recent publications is assumed.

  17. The oceanic cycle and global atmospheric budget of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, P.S.

    1994-12-31

    A significant portion of stratospheric air chemistry is influenced by the existence of carbonyl sulfide (COS). This ubiquitous sulfur gas represents a major source of sulfur to the stratosphere where it is converted to sulfuric acid aerosol particles. Stratospheric aerosols are climatically important because they scatter incoming solar radiation back to space and are able to increase the catalytic destruction of ozone through gas phase reactions on particle surfaces. COS is primarily formed at the surface of the earth, in both marine and terrestrial environments, and is strongly linked to natural biological processes. However, many gaps in the understanding of the global COS cycle still exist, which has led to a global atmospheric budget that is out of balance by a factor of two or more, and a lack of understanding of how human activity has affected the cycling of this gas. The goal of this study was to focus on COS in the marine environment by investigating production/destruction mechanisms and recalculating the ocean-atmosphere flux.

  18. Carbonyl Sulfide for Tracing Carbon Fluxes Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, J. Elliott [Univ. of California, Merced, CA (United States); Berry, Joseph A. [Carnegie Inst. of Science, Stanford, CA (United States); Billesbach, Dave [Univ. of Nebraska, Lincoln, NE (United States); Torn, Margaret S [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zahniser, Mark [Aerodyne Research, Inc., Billerica, MA (United States); Seibt, Ulrike [Univ. of California, Los Angeles, CA (United States); Maseyk, Kadmiel [Pierre and Marie Curie Univ., Paris (France)

    2016-04-01

    The April-June 2012 campaign was located at the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility Southern Great Plains (SGP) site Central Facility and had three purposes. One goal was to demonstrate the ability of current instrumentation to correctly measure fluxes of atmospheric carbonyl sulfide (COS). The approach has been describe previously as a critical approach to advancing carbon cycle science1,2, but requires further investigation at the canopy scale to resolve ecosystem processes. Previous canopy-scale efforts were limited to data rates of 1Hz. While 1 Hz measurements may work in a few ecosystems, it is widely accepted that data rates of 10 to 20 Hz are needed to fully capture the exchange of traces gases between the atmosphere and vegetative canopy. A second goal of this campaign was to determine if canopy observations could provide information to help interpret the seasonal double peak in airborne observations at SGP of CO2 and COS mixing ratios. A third goal was to detect potential sources and sinks of COS that must be resolved before using COS as a tracer of gross primary productivity (GPP).

  19. Regional-Scale Carbon Flux Partitioning Using Atmospheric Carbonyl Sulfide

    Science.gov (United States)

    Abu-Naser, M.; Campbell, J. E.; Berry, J. A.

    2011-12-01

    Simultaneous analysis of atmospheric concentrations of carbonyl sulfide (COS) and carbon dioxide (CO2) has been proposed as an approach to partitioning gross primary production and respiration fluxes at regional and global scales. The basis for this approach was that the observation and regional gradients in atmospheric CO2 are dominated by net ecosystem fluxes while regional gradients in atmospheric COS are dominated by GPP-related plant uptake. Here we investigate the spatial and temporal gradients in airborne COS and CO2 measurements in comparison to flux estimates from ecosystem models and eddy covariance methods over North America. The spatial gradients in the ecosystem relative uptake (ERU), the normalized ratio of COS and CO2 vertical gradients, were consistent with the theoretical relationship to flux estimates from ecosystem models and eddy covariance methods. The seasonality of the gross primary productivity flux estimates was consistent with airborne observations in the midwestern region but had mixed results in the southeastern region. Inter-annual changes in the ERU and regional drought index data suggested a potential relationship between drought stress and low ratios of gross primary production to net ecosystem exchange.

  20. Heterogeneous oxidation of carbonyl sulfide on mineral oxides

    Institute of Scientific and Technical Information of China (English)

    LIU YongChun; LIU JunFeng; HE Hong; YU YunBo; XUE Li

    2007-01-01

    Heterogeneous oxidation of carbonyl sulfide (OCS) on mineral oxides including SiO2, Fe2O3, CaO, MgO, ZnO and TiO2, which are the main components of atmospheric particles, were investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS), ion chromatography (IC), temperature-programmed desorption (TPD), X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) methods. The main products and intermediates of the heterogeneous oxidation of OCS on these oxides were identified with in situ DRIFTS and IC. The reaction mechanism and kinetics were also discussed. It is found that the reaction mechanism on these mineral oxides is the same as that on Al2O3 for the same final products and the intermediates at room temperature. Namely, OCS can be catalytically oxidized to produce surface SO42- species and gaseous CO2 through the surface hydrogen thiocarbonate (HSCO2-) and HSO3- species. The activity series for heterogeneous oxidation of OCS follows: Al2O3 ≈ CaO>MgO>TiO2 ≈ ZnO>Fe2O3>SiO2. The specific area, basic hydroxyl and surface basicity of these oxides have effect on the reactivity. This study suggests that heterogeneous reactions of OCS on mineral dust may be an unneglectable sink of OCS.

  1. Teratogenicity and embryotoxicity of nickel carbonyl in Syrian hamsters

    Energy Technology Data Exchange (ETDEWEB)

    Sunderman, F.W. Jr.; Shen, S.K.; Reid, M.C.; Allpass, P.R.

    1980-01-01

    Nickel carbonyl was administered to groups of pregnant hamsters by inhalation on days 4, 5, 6, 7, or 8 of gestation. The dams were killed on day 15 of gestation, and the fetuses were examined for malformations. Exposure to Ni(CO)/sub 4/ on days 4 or 5 of gestation resulted in malformation in 5.5% and 5.8% of the progeny, respectively. Progeny included 9 fetuses with cystic lungs, 7 fetuses with exencephaly, 1 fetus with exencephaly plus fused rib and 1 fetus with anophthalmia plus cleft palate. Hemorrhages into serious cavities were found. In progeny of dams exposed to Ni(CO)/sub 4/ on days 6 or 7 of gestation, there was 1 fetus with fused ribs and there were 2 fetuses with hydronephrosis. In another experiment, pregnant hamsters were exposed to inhalation of Ni(CO)/sub 4/ on day 5 of gestation; these dams were permitted to deliver their litters and to nurse their pups. There was no significant difference in the average number of live pups in the Ni(CO)/sub 4/-exposed litters compared to control litters. Neonatal mortality was increased in Ni(CO)/sub 4/-exposed litters. This study demonstrates that Ni(CO)/sub 4/ is teratogenic and embryotoxic in Syrian hamsters.

  2. Carbonyl sulfide uptake and chloroform emissions from an Arctic site

    Science.gov (United States)

    Elkins, J. W.; Dutton, G. S.; Montzka, S. A.; Nance, J. D.; Hall, B. D.; Thoning, K. W.; Miller, J. B.; White, J.; Vaugh, B.; Manning, A.

    2008-12-01

    The Arctic Region is most sensitive to future climate change. Quantifying emissions and sinks of many important biogenic trace gases there may become important indicators of potential climate feedback. Once snowmelt at Pt. Barrow, Alaska (77o N) occurs, ground cover is exposed by sunlight and higher temperatures, then photosynthesis starts up. Peaks of chloroform (CHCl3) appear throughout the summer from southerly-based air masses based over northern Alaska and northwest Canada. Carbonyl sulfide (COS) undergoes uptake throughout the summer season through the same enzymes that uptake carbon dioxide (CO2). We will calculate the footprint of emissions of CHCl3 and uptake of COS using high frequency in situ observations, and the NAME and FLEXPART models. Previous studies show a large source of CHCl3 (8% of the total budget) may be coming from soils in high latitude pine forests. We will examine emissions of CHCl3 to see whether or not they are coming from the tundra just south of Pt. Barrow. We will identify the regions for uptake of COS and CO2 from the footprint generated from the models.

  3. Degradation of ambient carbonyl sulfide by Mycobacterium spp. in soil.

    Science.gov (United States)

    Kato, Hiromi; Saito, Masahiko; Nagahata, Yoshiko; Katayama, Yoko

    2008-01-01

    The ability to degrade carbonyl sulfide (COS) was confirmed in seven bacterial strains that were isolated from soil, without the addition of COS. Comparative 16S rRNA gene sequence analysis indicated that these isolates belonged to the genera Mycobacterium, Williamsia and Cupriavidus. For example, Mycobacterium sp. strain THI401, grown on PYG agar medium, was able to degrade an initial level of 30 parts per million by volume COS within 1 h, while 60 % of the initial COS was decreased by abiotic conversion in 30 h. Considering natural COS flux between soil and the atmosphere, COS degradation by these bacteria was confirmed at an ambient level of 500 parts per trillion by volume (p.p.t.v.), using sterilized soil to cultivate the bacterium. Autoclave sterilization of soil resulted in a small amount of COS emission, while Mycobacterium spp. degraded COS at a faster rate than it was emitted from the soil, and reduced the COS mixing ratio to a level that was lower than the ambient level: THI401 degraded COS from an initial level of 530 p.p.t.v. to a level of 330 p.p.t.v. in 30 h. These results provide experimental evidence of microbial activity in soil as a sink for atmospheric COS.

  4. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Schindler, Matthias, E-mail: matthias.schindler@physik.uni-erlangen.de; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-15

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO{sub 2} and reduced to graphite to determine {sup 14}C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  5. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    Science.gov (United States)

    Schindler, Matthias; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander

    2016-05-01

    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO2 and reduced to graphite to determine 14C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  6. Protective mechanisms of Cucumis sativus in diabetes-related models of oxidative stress and carbonyl stress

    Directory of Open Access Journals (Sweden)

    Himan Heidari

    2016-03-01

    Conclusion: It can be concluded that C. sativus has protective effects in diabetes complications and can be considered a safe and suitable candidate for decreasing the oxidative stress and carbonyl stress that is typically observed in diabetes mellitus.

  7. A carbonyl iron/carbon fiber material for electromagnetic wave absorption.

    Science.gov (United States)

    Youh, Meng-Jey; Wu, Hung-Chih; Lin, Wang-Hua; Chiu, Sheng-Cheng; Huang, Chien-Fa; Yu, Hsin-Chih; Hsu, Jen-Sung; Li, Yuan-Yao

    2011-03-01

    A carbonyl iron/carbon fiber material consisting of carbon fibers grown on micrometer-sized carbonyl iron sphere, was synthesized by chemical vapor deposition using a mixture of C2H2 and H2. The hollow-core carbon fibers (outer diameter: 140 nm and inner diameter: 40 nm) were composed of well-ordered graphene layers which were almost parallel to the long axis of the fibers. A composite (2 mm thick) consisting of the carbonyl iron/carbon fibers and epoxy resin demonstrated excellent electromagnetic (EM) wave absorption. Minimum reflection losses of -36 dB (99.95% of EM wave absorption) at 7.6 GHz and -32 dB (99.92% of EM wave absorption) at 34.1 GHz were achieved. The well-dispersed and network-like carbon fibers in the resin matrix affected the dielectric loss of the EM wave while the carbonyl iron affected the magnetic loss.

  8. Corrosion inhibition of α,β-unsaturated carbonyl compounds on steel in acid medium

    Institute of Scientific and Technical Information of China (English)

    Gao Jiancun; Weng Yongji; Salitanate; Feng Li; Yue Hong

    2009-01-01

    Corrosion inhibition of three α,β-unsaturated carbonyl compounds on N80 steel at high temperature and in concentrated acid medium was evaluated, and the inhibition mechanism was investigated.The results proved that both cinnamaidehyde and benzalacetone had an evident anticorrosion effect and could reduce the corrosion of steel effectively in acid medium, α,β-unsaturated carbonyl compounds with a benzene ring structure had good adsorption on steel surface.The experiments proved that polymerization of α,β-unsaturated carbonyl compounds on the steel surface at a high temperature and in concentrated acid medium resulted in a good corrosion inhibiting effect, which was attributed to the structures of α,β-unsaturated carbonyl compounds.

  9. Efficient and selective α-bromination of carbonyl compounds with N-bromosuccinimide under microwave

    KAUST Repository

    Guan, Xiao-Yu

    2014-02-07

    A highly efficient method for the synthesis of α-halocarbonyl compounds has been achieved via selective monobromination of aromatic and aliphatic carbonyl compounds with N-bromosuccinimide catalyzed by p-toluenesulfonic acid under microwave irradiation within 30 min.

  10. Incorporating Cobalt Carbonyl Moieties onto Ethynylthiophene-Based Dithienylcyclopentene Switches. 1. Photochemistry

    NARCIS (Netherlands)

    Harvey, Emma C.; Areephong, Jetsuda; Cafolla, Attilio A.; Long, Conor; Browne, Wesley R.; Pryce, Mary T.; Feringa, Bernard

    2014-01-01

    The synthesis and characterization of a series of dithienyl perhydro- and perfluorocyclopentene photochromic molecular switches appended with cobalt carbonyl binding 3-ethynylthiophene and phenyl-3-ethynylthiophene substituents are reported. Their photochromic properties, fatigue resistance, and the

  11. Efficient alpha-Methylenation of Carbonyl Compounds in Ionic Liquids at Room Temperature

    OpenAIRE

    Vale, JA; Zanchetta, DF; Moran, PJS; RODRIGUES, JAR

    2009-01-01

    The application of several 1-butyl-3-methylimidazolium (BMIM) salt ionic liquids as solvent in the alpha-methylenation of carbonyl compounds at room temperature is reported. The ionic liquid [BMIM][NTf(2)] gave a clean reaction in a short time and good yields of several alpha-methylene carbonyl compounds. This ionic liquid was reused without affecting the reaction rates or yields over seven runs.

  12. Measurement of airborne carbonyls using an automated sampling and analysis system.

    Science.gov (United States)

    Aiello, Mauro; McLaren, Robert

    2009-12-01

    Based upon the well established method of derivitization with 2,4-dinitrophenylhydrazine, an instrument was developed for ambient measurement of carbonyls with significantly improved temporal resolution and detection limits through automation, direct injection, and continuous use of a single microsilica DNPH cartridge. Kinetic experiments indicate that the derivitization reaction on the cartridge is fast enough for continuous measurements with 50 min air sampling. Reaction efficiencies measured on the cartridge were 100% for the carbonyls tested, including formaldehyde, acetaldehyde, propanal, acetone, and benzaldehyde. Transmission of the carbonyls through an ozone scrubber (KI) were in the range of 97-101%. Blank levels and detection limits were lower than those obtainable with conventional DNPH methods by an order of magnitude or greater. Mixing ratio detection limits of carbonyls in ambient air were 38-73 ppt for a 50 min air sample (2.5 L). The instrument made continuous measurements of carbonyls on a 2 h cycle over a period of 10 days during a field study in southwestern Ontario. Median mixing ratios were 0.58 ppb formaldehyde; 0.29 ppb acetaldehyde; 1.14 ppb acetone; and 0.45 ppb glyoxal. Glyoxal shows a significant correlation with ozone and zero intercept, consistent with a secondary source and minor direct source to the atmosphere. The method should easily be extendable to the detection of other low molecular weight carbonyls that have been previously reported using the DNPH technique.

  13. Oxidative Stress and Carbonyl Lesions in Ulcerative Colitis and Associated Colorectal Cancer

    Directory of Open Access Journals (Sweden)

    Zhiqi Wang

    2016-01-01

    Full Text Available Oxidative stress has long been known as a pathogenic factor of ulcerative colitis (UC and colitis-associated colorectal cancer (CAC, but the effects of secondary carbonyl lesions receive less emphasis. In inflammatory conditions, reactive oxygen species (ROS, such as superoxide anion free radical (O2∙-, hydrogen peroxide (H2O2, and hydroxyl radical (HO∙, are produced at high levels and accumulated to cause oxidative stress (OS. In oxidative status, accumulated ROS can cause protein dysfunction and DNA damage, leading to gene mutations and cell death. Accumulated ROS could also act as chemical messengers to activate signaling pathways, such as NF-κB and p38 MAPK, to affect cell proliferation, differentiation, and apoptosis. More importantly, electrophilic carbonyl compounds produced by lipid peroxidation may function as secondary pathogenic factors, causing further protein and membrane lesions. This may in turn exaggerate oxidative stress, forming a vicious cycle. Electrophilic carbonyls could also cause DNA mutations and breaks, driving malignant progression of UC. The secondary lesions caused by carbonyl compounds may be exceptionally important in the case of host carbonyl defensive system deficit, such as aldo-keto reductase 1B10 deficiency. This review article updates the current understanding of oxidative stress and carbonyl lesions in the development and progression of UC and CAC.

  14. Direct photolysis of carbonyl compounds dissolved in cloud and fog droplets

    Science.gov (United States)

    Epstein, S. A.; Tapavicza, E.; Furche, F.; Nizkorodov, S. A.

    2013-04-01

    Gas phase photolysis is an important tropospheric sink for many carbonyl compounds, however the significance of direct photolysis of carbonyl compounds dissolved in cloud and fog droplets is uncertain. We develop a theoretical approach to assess the importance of aqueous photolysis for a series of carbonyls that possess carboxyl and hydroxyl functional groups by comparison with rates of other atmospheric processes. We use computationally and experimentally derived Henry's law parameters, hydration equilibrium parameters, aqueous hydroxyl radical (OH) rate constants, and optical extinction coefficients to identify types of compounds that will not have competitive aqueous photolysis rates. We also present molecular dynamics simulations of atmospherically relevant carbonyl compounds designed to estimate gas and aqueous phase extinction coefficients. In addition, experiments designed to measure the photolysis rate of glyceraldehyde, an atmospherically relevant water soluble organic compound, reveal that aqueous quantum yields are highly molecule-specific and cannot be extrapolated from measurements of structurally similar compounds. We find that only three out of the 92 carbonyl compounds investigated, pyruvic acid, 3-oxobutanoic acid, and 3-oxopropanoic acid, may have aqueous photolysis rates that exceed the rate of oxidation by dissolved OH. For almost all carbonyl compounds lacking α, β conjugation, atmospheric removal by direct photolysis in cloud and fog droplets can be neglected.

  15. A biotin enrichment strategy identifies novel carbonylated amino acids in proteins from human plasma.

    Science.gov (United States)

    Havelund, Jesper F; Wojdyla, Katarzyna; Davies, Michael J; Jensen, Ole N; Møller, Ian Max; Rogowska-Wrzesinska, Adelina

    2017-03-06

    Protein carbonylation is an irreversible protein oxidation correlated with oxidative stress, various diseases and ageing. Here we describe a peptide-centric approach for identification and characterisation of up to 14 different types of carbonylated amino acids in proteins. The modified residues are derivatised with biotin-hydrazide, enriched and characterised by tandem mass spectrometry. The strength of the method lies in an improved elution of biotinylated peptides from monomeric avidin resin using hot water (95°C) and increased sensitivity achieved by reduction of analyte losses during sample preparation and chromatography. For the first time MS/MS data analysis utilising diagnostic biotin fragment ions is used to pinpoint sites of biotin labelling and improve the confidence of carbonyl peptide assignments. We identified a total of 125 carbonylated residues in bovine serum albumin after extensive in vitro metal ion-catalysed oxidation. Furthermore, we assigned 133 carbonylated sites in 36 proteins in native human plasma protein samples. The optimised workflow enabled detection of 10 hitherto undetected types of carbonylated amino acids in proteins: aldehyde and ketone modifications of leucine, valine, alanine, isoleucine, glutamine, lysine and glutamic acid (+14Da), an oxidised form of methionine - aspartate semialdehyde (-32Da) - and decarboxylated glutamic acid and aspartic acid (-30Da).

  16. Protein carbonylation, protein aggregation and neuronal cell death in a murine model of multiple sclerosis

    Science.gov (United States)

    Dasgupta, Anushka

    Many studies have suggested that oxidative stress plays an important role in the pathophysiology of both multiple sclerosis (MS) and its animal model experimental autoimmune encephalomyelitis (EAE). Yet, the mechanism by which oxidative stress leads to tissue damage in these disorders is unclear. Recent work from our laboratory has revealed that protein carbonylation, a major oxidative modification caused by severe and/or chronic oxidative stress conditions, is elevated in MS and EAE. Furthermore, protein carbonylation has been shown to alter protein structure leading to misfolding/aggregation. These findings prompted me to hypothesize that carbonylated proteins, formed as a consequence of oxidative stress and/or decreased proteasomal activity, promote protein aggregation to mediate neuronal apoptosis in vitro and in EAE. To test this novel hypothesis, I first characterized protein carbonylation, protein aggregation and apoptosis along the spinal cord during the course of myelin-oligodendrocyte glycoprotein (MOG)35-55 peptide-induced EAE in C57BL/6 mice [Chapter 2]. The results show that carbonylated proteins accumulate throughout the course of the disease, albeit by different mechanisms: increased oxidative stress in acute EAE and decreased proteasomal activity in chronic EAE. I discovered not only that there is a temporal correlation between protein carbonylation and apoptosis but also that carbonyl levels are significantly higher in apoptotic cells. A high number of juxta-nuclear and cytoplasmic protein aggregates containing the majority of the oxidized proteins are also present during the course of EAE, which seems to be due to reduced autophagy. In chapter 3, I show that when gluthathione levels are reduced to those in EAE spinal cord, both neuron-like PC12 (nPC12) cells and primary neuronal cultures accumulate carbonylated proteins and undergo cell death (both by necrosis and apoptosis). Immunocytochemical and biochemical studies also revealed a temporal

  17. Fast retrievals of tropospheric carbonyl sulfide with IASI

    Science.gov (United States)

    Vincent, R. Anthony; Dudhia, Anu

    2017-02-01

    Iterative retrievals of trace gases, such as carbonyl sulfide (OCS), from satellites can be exceedingly slow. The algorithm may even fail to keep pace with data acquisition such that analysis is limited to local events of special interest and short time spans. With this in mind, a linear retrieval scheme was developed to estimate total column amounts of OCS at a rate roughly 104 times faster than a typical iterative retrieval. This scheme incorporates two concepts not utilized in previously published linear estimates. First, all physical parameters affecting the signal are included in the state vector and accounted for jointly, rather than treated as effective noise. Second, the initialization point is determined from an ensemble of atmospheres based on comparing the model spectra to the observations, thus improving the linearity of the problem. All of the 2014 data from the Infrared Atmospheric Sounding Interferometer (IASI), instruments A and B, were analysed and showed spatial features of OCS total columns, including depletions over tropical rainforests, seasonal enhancements over the oceans, and distinct OCS features over land. Error due to assuming linearity was found to be on the order of 11 % globally for OCS. However, systematic errors from effects such as varying surface emissivity and extinction due to aerosols have yet to be robustly characterized. Comparisons to surface volume mixing ratio in situ samples taken by NOAA show seasonal correlations greater than 0.7 for five out of seven sites across the globe. Furthermore, this linear scheme was applied to OCS, but may also be used as a rapid estimator of any detectable trace gas using IASI or similar nadir-viewing instruments.

  18. Intramolecular Hydrogen Bond in Biologically Active o-Carbonyl Hydroquinones

    Directory of Open Access Journals (Sweden)

    Maximiliano Martínez-Cifuentes

    2014-07-01

    Full Text Available Intramolecular hydrogen bonds (IHBs play a central role in the molecular structure, chemical reactivity and interactions of biologically active molecules. Here, we study the IHBs of seven related o-carbonyl hydroquinones and one structurally-related aromatic lactone, some of which have shown anticancer and antioxidant activity. Experimental NMR data were correlated with theoretical calculations at the DFT and ab initio levels. Natural bond orbital (NBO and molecular electrostatic potential (MEP calculations were used to study the electronic characteristics of these IHB. As expected, our results show that NBO calculations are better than MEP to describe the strength of the IHBs. NBO energies (∆Eij(2 show that the main contributions to energy stabilization correspond to LPàσ* interactions for IHBs, O1…O2-H2 and the delocalization LPàπ* for O2-C2 = Cα(β. For the O1…O2-H2 interaction, the values of ∆Eij(2 can be attributed to the difference in the overlap ability between orbitals i and j (Fij, instead of the energy difference between them. The large energy for the LP O2àπ* C2 = Cα(β interaction in the compounds 9-Hydroxy-5-oxo-4,8, 8-trimethyl-l,9(8H-anthracenecarbolactone (VIII and 9,10-dihydroxy-4,4-dimethylanthracen-1(4H-one (VII (55.49 and 60.70 kcal/mol, respectively when compared with the remaining molecules (all less than 50 kcal/mol, suggests that the IHBs in VIII and VII are strongly resonance assisted.

  19. Metabolism of bupropion by carbonyl reductases in liver and intestine.

    Science.gov (United States)

    Connarn, Jamie N; Zhang, Xinyuan; Babiskin, Andrew; Sun, Duxin

    2015-07-01

    Bupropion's metabolism and the formation of hydroxybupropion in the liver by cytochrome P450 2B6 (CYP2B6) has been extensively studied; however, the metabolism and formation of erythro/threohydrobupropion in the liver and intestine by carbonyl reductases (CR) has not been well characterized. The purpose of this investigation was to compare the relative contribution of the two metabolism pathways of bupropion (by CYP2B6 and CR) in the subcellular fractions of liver and intestine and to identify the CRs responsible for erythro/threohydrobupropion formation in the liver and the intestine. The results showed that the liver microsome generated the highest amount of hydroxybupropion (Vmax = 131 pmol/min per milligram, Km = 87 μM). In addition, liver microsome and S9 fractions formed similar levels of threohydrobupropion by CR (Vmax = 98-99 pmol/min per milligram and Km = 186-265 μM). Interestingly, the liver has similar capability to form hydroxybupropion (by CYP2B6) and threohydrobupropion (by CR). In contrast, none of the intestinal fractions generate hydroxybupropion, suggesting that the intestine does not have CYP2B6 available for metabolism of bupropion. However, intestinal S9 fraction formed threohydrobupropion to the extent of 25% of the amount of threohydrobupropion formed by liver S9 fraction. Enzyme inhibition and Western blots identified that 11β-dehydrogenase isozyme 1 in the liver microsome fraction is mainly responsible for the formation of threohydrobupropion, and in the intestine AKR7 may be responsible for the same metabolite formation. These quantitative comparisons of bupropion metabolism by CR in the liver and intestine may provide new insight into its efficacy and side effects with respect to these metabolites.

  20. Soil fluxes of carbonyl sulfide (COS) across four distinct ecosystems

    Science.gov (United States)

    Sun, W.; Maseyk, K. S.; Lett, C.; Juarez, S.; Kooijmans, L.; Mammarella, I.; Vesala, T.; Chen, H.; Seibt, U.

    2015-12-01

    Soils are additional but poorly resolved sinks of carbonyl sulfide (COS) in terrestrial ecosystems. COS has been proposed as a tracer for quantifying gross photosynthesis based on the coupled stomatal uptake of COS and CO2. But applying this tracer requires the soil COS flux to be subtracted from the ecosystem flux to obtain the actual plant flux. To simulate soil COS fluxes, we have built a 1-D diffusion-reaction model accounting for vertical transport in the soil, microbial sinks and sources, and a litter layer. Uptake and production of COS in the soil column are linked with soil temperature and moisture through empirical functions adapted from enzyme kinetics and lab incubations. We have measured soil COS fluxes and the related soil variables in four distinct ecosystems: a wheat field (Southern Great Plains, OK, USA), an oak woodland (Santa Monica Mountains, CA, USA), a tropical rainforest (La Selva Biological Station, Costa Rica) and a boreal pine forest (Hyytiälä, Finland). Across all sites, a lower soil temperature and a humid climate are generally favorable to soil COS uptake. Strong COS emissions were observed in the wheat field at high soil temperatures after harvesting but were absent in other ecosystems, indicating that COS exchange may behave differently in agricultural soils. We simulated the soil fluxes in all ecosystems using the diffusion-reaction model, and optimized the source/sink strength parameters with field data. The optimized model provides insights that are not attainable from data analysis alone: For example, the wheat field soil must have continued uptake activity even when it showed net emissions, and leaf litter contributed dominantly to the COS sink after rain in the oak woodland. We expect the new model to be useful for simulating global soil COS fluxes as field data on soil fluxes from a broader range of ecosystems become available.

  1. Organometallic and Bioorganometallic Chemistry - Ferrocene and Metal Carbonyls

    Directory of Open Access Journals (Sweden)

    Čakić Semenčić, M.

    2011-02-01

    Full Text Available Organometallic chemistry deals with compounds containing metal-carbon bonds. Basic organometallics derived from the s- and p-block metals (containing solely σ-bonds were understood earlier, while organometallic chemistry of the d- and f-block has developed much more recently. These compounds are characterized by three types of M-C bonds (σ, π and δand their structures are impossible to deduce by chemical means alone; fundamental advances had to await the development of X-ray diffraction, as well as IR- and NMR-spectroscopy. On the other hand, elucidation of the structure of e. g. vitamin B12 and ferrocene (discovered in 1951 contributed to progress in these instrumental analytical methods, influencing further phenomenal success of transition-metal organometallic chemistry in the second half of the twentieth century. The most thoroughly explored fields of application of organometallics were in the area of catalysis, asymmetric synthesis, olefin metathesis, as well as organic synthesis and access to new materials and polymers.The most usual ligands bound to d- and f-metals are carbon monoxide, phosphines, alkyls, carbenes and arenes, and in this review the bonding patterns in the metal carbonyls and ferrocene are elaborated. The common characteristics of these two classes are two-component bonds. The CO-M bonds include (i donation from ligand HOMO to vacant M d-orbitals (σ-bond, and (ii back-donation from the filled M d-orbitals in the ligand LUMO (π-bond. Similar (but much more complicated ferrocene contains delocalized bonds consisting of electron donation from Cp to Fe (σ-bonds- and π-bonding and δ-back-bonding from metal to Cp. In such a way ferrocene, i. e. (η5-Cp2Fe contains 18 bonding electrons giving to this compound "superaromatic" properties in the sense of stability and electrophilic substitution. In contrast to benzenoid aromatic compounds reactions in two Cp-rings can occur giving homo- and heteroannularly mono-, two-… per

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

    Science.gov (United States)

    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.

  3. Proteomic identification of carbonylated proteins in F344 rat hippocampus after 1-bromopropane exposure

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhenlie [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan); Department of Toxicology, Guangdong Prevention and Treatment Center for Occupational Diseases, Guangzhou 510‐300 (China); Ichihara, Sahoko [Graduate School of Regional Innovation Studies, Mie University, Tsu 514‐8507 (Japan); Oikawa, Shinji [Department of Environmental and Molecular Medicine, Mie University Graduate School of Medicine, Mie 514‐8507 (Japan); Chang, Jie; Zhang, Lingyi; Subramanian, Kaviarasan; Mohideen, Sahabudeen Sheik [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan); Ichihara, Gaku, E-mail: gak@med.nagoya-u.ac.jp [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan)

    2012-08-15

    1-Bromopropane (1-BP) is neurotoxic in both experimental animals and humans. Previous proteomic analysis of rat hippocampus implicated alteration of protein expression in oxidative stress, suggesting that oxidative stress plays a role in 1-BP-induced neurotoxicity. To understand this role at the protein level, we exposed male F344 rats to 1-BP at 0, 400, or 1000 ppm for 8 h/day for 1 week or 4 weeks by inhalation and quantitated changes in hippocampal protein carbonyl using a protein carbonyl assay, two-dimensional gel electrophoresis (2-DE), immunoblotting, and matrix-assisted laser-desorption ionization time-of-flight mass spectrometry (MALDI-TOF-TOF/MS). Hippocampal reactive oxygen species and protein carbonyl were significantly increased, demonstrating 1-BP-associated induction of oxidative stress and protein damage. MALDI-TOF-TOF/MS identified 10 individual proteins with increased carbonyl modification (p < 0.05; fold-change ≥ 1.5). The identified proteins were involved in diverse biological processes including glycolysis, ATP production, tyrosine catabolism, GTP binding, guanine degradation, and neuronal metabolism of dopamine. Hippocampal triosephosphate isomerase (TPI) activity was significantly reduced and negatively correlated with TPI carbonylation (p < 0.001; r = 0.83). Advanced glycation end-product (AGE) levels were significantly elevated both in the hippocampus and plasma, and hippocampal AGEs correlated negatively with TPI activity (p < 0.001; r = 0.71). In conclusion, 1-BP-induced neurotoxicity in the rat hippocampus seems to involve oxidative damage of cellular proteins, decreased TPI activity, and elevated AGEs. -- Highlights: ► 1-BP increases hippocampal ROS levels and hippocampal and plasma protein carbonyls. ► 1-BP increases TPI carbonylation and decreases TPI activity in the hippocampus. ► 1-BP increases hippocampal and plasma AGE levels.

  4. Positive trends in Southern Hemisphere observations of carbonyl sulfide

    Science.gov (United States)

    Kremser, Stefanie; Jones, Nicholas; Smale, Dan; Palm, Mathias; Lejeune, Bernard; Wang, Yuting; Deutscher, Nicholas

    2016-04-01

    Carbonyl sulfide (OCS; lifetime of about 5.7 years) is the longest lived reduced sulfur-containing gas in the atmosphere. The primary source of OCS is the ocean, which is both a direct source (through OCS emission) and an indirect source (due to oxidation of carbon disulfide, CS2, and dimethyl sulfide). Other natural sources of OCS include volcanic outgassing and direct fluxes from wetland regions. The removal of OCS from the atmosphere is dominated by soil and vegetation uptake, with minor contributions from reactions with the hydroxyl radical. Small anthropogenic sources of OCS are coal combustion, biomass burning, and aluminum production. A dominant indirect source results from CS2 emissions from the rayon industry. Transport of tropospheric OCS to the stratosphere during volcanically quiescent periods has been suggested to contribute sulfur to the stratospheric aerosol layer which affects atmospheric radiative balance. If, however, production of stratospheric aerosols from OCS oxidation is smaller than typical estimates, this OCS contribution would be overestimated. The magnitude of the OCS flux to the stratosphere is currently not well quantified as is the relative contribution of OCS to background aerosol loading. While earlier model simulations indicate OCS fluxes into the atmosphere exceeding removal, past total column observations of OCS show no significant trend. Analysis of tropospheric OCS columns at Arrival Heights (Antarctica) and Lauder (New Zealand) show strong positive trends from 2001-2008 followed by weaker trends to 2015, with unexpected temporal coherence. Since trends in ocean and land sources/sinks at these two sites, respectively, are unlikely to be similar, the coherence in trend structure likely results from changes in transport of OCS from the tropics to middle and high latitudes. Potential causes for OCS increases are (i) increases in tropical lower stratospheric OCS and/or (ii) strengthening of the large-scale circulation which

  5. Strong soil source of carbonyl sulfide in an agricultural field

    Science.gov (United States)

    Maseyk, K. S.; Seibt, U.; Berry, J. A.; Billesbach, D. P.; Campbell, J.; Torn, M. S.

    2012-12-01

    A promising new approach to constrain biosphere-atmosphere carbon and water exchange is the use of carbonyl sulfide (COS). COS is taken up by leaves via the same pathway as CO2, leading to a close coupling of vegetation COS and CO2 fluxes during photosynthesis. Therefore it has been proposed that the gross fluxes of photosynthesis and respiration can be quantified through the concurrent measurements of COS and CO2. A necessary requirement for this approach at ecosystem and continental scales are estimates of soil COS fluxes. Soil is largely considered a sink for COS, but our knowledge of in situ soil COS fluxes remains very limited. We measured soil COS fluxes in a wheat field in Oklahoma from April to June 2012, using a novel combination of an automated soil chamber coupled to a COS laser analyzer. We provide the first continuous record of soil COS fluxes under natural conditions, and report on a phenomenon that has not been observed before. In contrast to the majority of published results, we found that the agricultural soil was a strong source of COS under most conditions during the campaign. The COS flux over the study period was highly correlated with soil temperature. Up to a soil temperature of around 15°C, the soil acted as a COS sink. Above 15°C, it acted a source of COS, with fluxes of up to 25 pmol m-2 s-1. To locate the source of the COS production, we investigated different soil components. Wheat roots were found to be emitting COS under all conditions. Root-free soil was a COS sink up to a soil temperature of around 25°C, but turned into a COS source at higher soil temperatures. We also observed COS production from the roots of several other species, indicating that this may be a widespread phenomenon. Using eddy covariance data of COS and CO2 that was collected concurrently with the soil measurements, we also demonstrate how the soil COS source can be taken into account when partitioning net ecosystem exchange into photosynthesis and respiration.

  6. Fructose-Induced Carbonyl/Oxidative Stress in S. cerevisiae: Involvement of TOR.

    Science.gov (United States)

    Valishkevych, Bohdana V; Vasylkovska, Ruslana A; Lozinska, Liudmyla M; Semchyshyn, Halyna M

    2016-01-01

    The TOR (target of rapamycin) signaling pathway first described in the budding yeast Saccharomyces cerevisiae is highly conserved in eukaryotes effector of cell growth, longevity, and stress response. TOR activation by nitrogen sources, in particular amino acids, is well studied; however its interplay with carbohydrates and carbonyl stress is poorly investigated. Fructose is a more potent glycoxidation agent capable of producing greater amounts of reactive carbonyl (RCS) and oxygen species (ROS) than glucose. The increased RCS/ROS production, as a result of glycoxidation in vivo, is supposed to be involved in carbonyl/oxidative stress, metabolic disorders, and lifespan shortening of eukaryotes. In this work we aim to expand our understanding of how TOR is involved in carbonyl/oxidative stress caused by reducing monosaccharides. It was found that in fructose-grown compared with glucose-grown cells the level of carbonyl/oxidative stress markers was higher. The defects in the TOR pathway inhibited metabolic rate and suppressed generation of glycoxidation products in fructose-grown yeast.

  7. A cleavable biotin tagging reagent that enables the enrichment and identification of carbonylation sites in proteins.

    Science.gov (United States)

    Coffey, Chelsea M; Gronert, Scott

    2016-01-01

    The utility of a new, cleavable tag for identifying and enriching protein carbonyls is examined. Using a model system, human serum albumin modified with acrolein, the EZ-Link alkoxyamine-PEG4-SS-PEG4-biotin affinity tag, was tested for its ability to label protein carbonyls in proteomic analyses of protein carbonylation. The efficiency of the labeling was assayed and compared to standard biotin hydrazide reagents. The label was also tested in liquid chromatography-tandem mass spectrometry (LC/MS/MS) experiments. The quality of the fragmentation spectra was assessed and the relative detection efficiency of various modification sites was compared to standard biotin hydrazide reagents. Finally, the viability of using the label with streptavidin bead enrichment protocols in a standard proteomics workflow was probed.

  8. Synthesis of Carbazoles and Carbazole-Containing Heterocycles via Rhodium-Catalyzed Tandem Carbonylative Benzannulations.

    Science.gov (United States)

    Song, Wangze; Li, Xiaoxun; Yang, Ka; Zhao, Xian-liang; Glazier, Daniel A; Xi, Bao-min; Tang, Weiping

    2016-04-01

    Polycyclic aromatic compounds are important constituents of pharmaceuticals and other materials. We have developed a series of Rh-catalyzed tandem carbonylative benzannulations for the synthesis of tri-, tetra-, and pentacyclic heterocycles from different types of aryl propargylic alcohols. These tandem reactions provide efficient access to highly substituted carbazoles, furocarbazoles, pyrrolocarbazoles, thiophenocarbazoles, and indolocarbazoles. While tricyclic heterocycles could be derived from vinyl aryl propargylic alcohols, tetra- and pentacyclic heterocycles were synthesized from diaryl propargylic alcohols. The tandem carbonylative benzannulation is initiated by a π-acidic rhodium(I) catalyst-mediated nucleophilic addition to alkyne to generate a key metal-carbene intermediate, which is then trapped by carbon monoxide to form a ketene species for 6π electrocyclization. Overall, three bonds and two rings are formed in all of these tandem carbonylative benzannulation reactions.

  9. Influence of the Dielectric Medium on the Carbonyl Infrared Absorption Peak of Acetylferrocene

    Directory of Open Access Journals (Sweden)

    F. López-Linares

    2005-02-01

    Full Text Available The solvent effect on the position of the carbonyl vibrational stretching ofacetylferrocene in aprotic media was studied in this work. The solvent-induced shifts in thisorganometallic compound were interpreted in terms of the alternative reaction field model(SCRF-MO proposed by Kolling. In contrast to the established trends for carbonyl groupsin organic systems, the results suggest that the continuum models for the reaction field arenot adequate and that the influence of dipolarity-polarizability described by aninhomogeneous coupling function θ (ε L(n 2 that assumes optical dielectric saturation isresponsible for the carbonyl band shift and, there is empirical evidence that the effect offield-induced intermolecular interaction on band shift, interpreted in terms of the van derWaals forces from the solvent, have a important contribution to this phenomena.

  10. Influence of carbonyl iron particle coating with silica on the properties of magnetorheological elastomers

    Science.gov (United States)

    Małecki, P.; Królewicz, M.; Hiptmair, F.; Krzak, J.; Kaleta, J.; Major, Z.; Pigłowski, J.

    2016-10-01

    In this paper, the influence of encapsulating carbonyl iron particles with various silica coatings on the properties of magnetorheological elastomers (MREs) was investigated. A soft styrene-ethylene-butylene-styrene thermoplastic elastomer was used as the composite’s polymer matrix. Spherical carbonyl iron powder (CIP) acted as the ferromagnetic filler. In order to improve the metal-polymer interaction, carbonyl iron particles were coated with two types of single and six types of double silica layers. The first layer was created through a TMOS or TEOS hydrolysis whereas the second one was composed of organosilanes. The mechanical properties of MREs containing 38.5 vol% of CIP were analysed under dynamic loading conditions. To investigate the magnetorheological effect in these composites, a 430 mT magnetic field, generated by an array of permanent magnets, was applied during testing. The results revealed that the magnetomechanical response of the MREs differs substantially, depending on the kind of particle coating.

  11. Ab initio determination of dark structures in radiationless transitions for aromatic carbonyl compounds.

    Science.gov (United States)

    Fang, Wei-Hai

    2008-03-01

    Mechanistic photodissociation of a polyatomic molecule has long been regarded as an intellectually challenging area of chemical physics, the results of which are relevant to atmospheric chemistry, biological systems, and many application fields. Carbonyl compounds play a unique role in the development of our understanding of the spectroscopy, photochemistry, and photophysics of polyatomic molecules and their photodissociation has been the subject of numerous studies over many decades. Upon irradiation, a molecule can undergo internal conversion (IC) and intersystem crossing (ISC) processes, besides photochemical and other photophysical processes. Transient intermediates formed in the IC and ISC radiationless processes, which are termed "dark", are not amenable to detection by conventional light absorption or emission. However, these dark intermediates play critical roles in IC and ISC processes and thus are essential to understanding mechanistic photochemistry of a polyatomic molecule. We have applied the multiconfiguration complete active space self-consistent field (CASSCF) method to determine the dark transient structures involved in radiationless processes for acetophenone and the related aromatic carbonyl compounds. The electronic and geometric structures predicted for the dark states are in a good agreement with those determined by ultrafast electron diffraction experiments. Intersection structure of different electronic states provides a very efficient "funnel" for the IC or ISC process. However, experimental determination of the intersection structure involved in radiationless transitions of a polyatomic molecule is impossible at present. We have discovered a minimum energy crossing point among the three potential energy surfaces (S1, T1, and T2) that appears to be common to a wide variety of aromatic carbonyl compounds with a constant structure. This new type of crossing point holds the key to understanding much about radiationless processes after

  12. Is carbonyl sulfide a precursor for carbon disulfide in vegetation and soil? Interconversion of carbonyl sulfide and carbon disulfide in fresh grain tissues in vitro.

    Science.gov (United States)

    Ren, Y

    1999-05-01

    The interconversion of carbonyl sulfide (COS) and carbon disulfide (CS(2)) was studied in the roots and shoots of barley and chickpeas. Ratios of conversion gases, K, 40 h after the addition of COS or CS(2) are recorded. The proportion of COS converted to each of CS(2), CO, and H(2)S and the proportion of CS(2) converted to COS were greater in roots than in shoots. More COS was converted to CS(2) than CS(2) to COS in roots and shoots of barley and chickpeas. The amount of COS converted to H(2)S and CO was 8 times the amount converted to CS(2) in barley and 3-4 times the amount in chickpeas. Carbonyl sulfide may be a precursor for CS(2) in vegetation and soil, just as the reverse is true in the atmosphere. These two different results might form a cycle of COS and CS(2).

  13. Impaired cardiac SIRT1 activity by carbonyl stress contributes to aging-related ischemic intolerance.

    Directory of Open Access Journals (Sweden)

    Chunhu Gu

    Full Text Available Reactive aldehydes can initiate protein oxidative damage which may contribute to heart senescence. Sirtuin 1 (SIRT1 is considered to be a potential interventional target for I/R injury management in the elderly. We hypothesized that aldehyde mediated carbonyl stress increases susceptibility of aged hearts to ischemia/reperfusion (I/R injury, and elucidate the underlying mechanisms with a focus on SIRT1. Male C57BL/6 young (4-6 mo and aged (22-24 mo mice were subjected to myocardial I/R. Cardiac aldehyde dehydrogenase (ALDH2, SIRT1 activity and protein carbonyls were assessed. Our data revealed that aged heart exhibited increased endogenous aldehyde/carbonyl stress due to impaired ALDH2 activity concomitant with blunted SIRT1 activity (P<0.05. Exogenous toxic aldehydes (4-HNE exposure in isolated cardiomyocyte verified that aldehyde-induced carbonyl modification on SIRT1 impaired SIRT1 activity leading to worse hypoxia/reoxygenation (H/R injury, which could all be rescued by Alda-1 (ALDH2 activator (all P<0.05. However, SIRT1 inhibitor blocked the protective effect of Alda-1 on H/R cardiomyocyte. Interestingly, myocardial I/R leads to higher carbonylation but lower activity of SIRT1 in aged hearts than that seen in young hearts (P<0.05. The application of Alda-1 significantly reduced the carbonylation on SIRT1 and markedly improved the tolerance to in vivo I/R injury in aged hearts, but failed to protect Sirt1(+/- knockout mice against myocardial I/R injury. This was verified by Alda-1 treatment improved postischemic contractile function recovery in ex vivo perfused aged but not in Sirt1(+/- hearts. Thus, aldehyde/carbonyl stress is accelerated in aging heart. These results provide a new insight that impaired cardiac SIRT1 activity by carbonyl stress plays a critical role in the increased susceptibility of aged heart to I/R injury. ALDH2 activation can restore this aging-related myocardial ischemic intolerance.

  14. Ab initio MO study of reaction mechanism for carbonyl migration of Co complex

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Ab initio method under the effective core potential (ECP) approximation is employed to study the reaction mechanism of carbonyl migration of the cycle of olefin hydroformylation catalyzed by a carbonyl cobalt HCo(CO)3 at Hartree-Fock (HF) level. The structures of the reactant, transition state and product for the reaction are determined. The energy of each stationary point is corrected at MP2/LAN2DZ//LANL2DZ+ZPE (zero-point energy) level. The calculated activation barrier is 28.89 kJ/mol.

  15. Formation and emissions of carbonyls during and following gas-phase ozonation of indoor materials

    DEFF Research Database (Denmark)

    Poppendieck, D.G.; Hubbard, H.F.; Weschler, Charles J.;

    2007-01-01

    from 1 to 20 mg m(-2), with most of the carbonyls being of lower molecular weight (C-1-C-4). In contrast, total BOBP mass released from wood-based products ranged from 20 to 100 mg m(-2), with a greater fraction of the BOBPs being heavier carbonyls (C-5-C-9). The total BOBP mass released during...... relatively high BOBP releases. The greatest overall BOBP mass releases were observed for three materials that building occupants might have significant contact with: paper, office partition, and medium density fiberboard, e.g., often used in office furniture. These materials also exhibited extended BOBP...

  16. Particle growth by acid-catalyzed heterogeneous reactions of organic carbonyls on preexisting aerosols.

    Science.gov (United States)

    Jang, Myoseon; Carroll, Brian; Chandramouli, Bharadwaj; Kamens, Richard M

    2003-09-01

    Aerosol growth by the heterogeneous reactions of different aliphatic and alpha,beta-unsaturated carbonyls in the presence/absence of acidified seed aerosols was studied in a 2 m long flow reactor (2.5 cm i.d.) and a 0.5-m3 Teflon film bag under darkness. For the flow reactor experiments, 2,4-hexadienal, 5-methyl-3-hexen-2-one, 2-cyclohexenone, 3-methyl-2-cyclopentenone, 3-methyl-2-cyclohexenone, and octanal were studied. The carbonyls were selected based on their reactivity for acid-catalyzed reactions, their proton affinity, and their similarity to the ring-opening products from the atmospheric oxidation of aromatics. To facilitate acid-catalyzed heterogeneous hemiacetal/acetal formation, glycerol was injected along with inorganic seed aerosols into the flow reactor system. Carbonyl heterogeneous reactions were accelerated in the presence of acid catalysts (H2SO4), leading to higher aerosol yields than in their absence. Aldehydes were more reactive than ketones for acid-catalyzed reactions. The conjugated functionality also resulted in higher organic aerosol yieldsthan saturated aliphatic carbonyls because conjugation with the olefinic bond increases the basicity of the carbonyl leading to increased stability of the protonated carbonyl. Aerosol population was measured from a series of sampling ports along the length of the flow reactor using a scanning mobility particle sizer. Fourier transform infrared spectrometry of either an impacted liquid aerosol layer or direct reaction of carbonyls as a thin liquid layer on a zinc selenide FTIR disk was employed to demonstrate the direct transformation of chemical functional groups via the acid-catalyzed reactions. These results strongly indicate that atmospheric multifunctional organic carbonyls, which are created by atmospheric photooxidation reactions, can contribute significantly to secondary organic aerosol formation through acid-catalyzed heterogeneous reactions. Exploratory studies in 25- and 190-m3 outdoor chambers

  17. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

    DEFF Research Database (Denmark)

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter

    2006-01-01

    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.......A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation....

  18. Photophysical properties of a synthetic, carbonyl-containing (N = 6+Cdbnd O) carotenoid analogue

    Science.gov (United States)

    Niedzwiedzki, Dariusz M.

    2014-05-01

    Retinyl-1 is a synthetic carotenoid analogue belonging to the retinal analogues family. It has six conjugated carbon-carbon double bonds with a carbonyl group conjugated to the π-electron system. Presence of the carbonyl group in vicinity of the conjugated carbon-carbon backbone leads to unique excited state properties that are extremely sensitive to solvent polarity and temperature. The simplicity of the synthesis of Retinyl-1 and ease of attachment to synthetic tetrapyrrole chromophores make Retinyl-1 attractive for use in artificial photosynthetic systems.

  19. Photophysical properties of a synthetic, carbonyl-containing (N=6+CO) carotenoid analogue

    Energy Technology Data Exchange (ETDEWEB)

    Niedzwiedzki, Dariusz M. [Washington Univ., St. Louis, MO (United States)

    2014-05-01

    Retinyl-1 is a synthetic carotenoid analogue belonging to the retinal analogues family. It has six conjugated carbon–carbon double bonds with a carbonyl group conjugated to the π-electron system. Presence of the carbonyl group in vicinity of the conjugated carbon–carbon backbone leads to unique excited state properties that are extremely sensitive to solvent polarity and temperature. The simplicity of the synthesis of Retinyl-1 and ease of attachment to synthetic tetrapyrrole chromophores make Retinyl-1 attractive for use in artificial photosynthetic systems.

  20. POLYMER—SUPPORTED RHODIUM CATALYSTS FOR CARBONYLATION OF METHYL ACETATE TO ACETIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    CHENDean; HUANGShizhuan; 等

    1993-01-01

    Two kinds of rhodium catalysts supported on cross-linked styrene-divinylbenzene copolymers containing bipyridine or o-phenylene diamine have been prepared and found to display high activity for methyl acetate carbonylation to form acetic anhydride,the activities are even higher than their homogeneous counterparts. XPS analysis was used to characterize the synthetic catalysts.The apparent activation parameters were determined to be Eα=73.3KJ/mol,ΔH≠=66.3KJ/mol,ΔS≠=-28.6eu.These parameters are very close to those in methanol carbonylation and imply to have analogous mechanism in both cases.

  1. Hydrolysis of Carbonyl Sulfide in Binary Mixture of Diethylene Glycol Diethyl Ether and Water

    Institute of Scientific and Technical Information of China (English)

    李新学; 刘迎新; 魏雄辉

    2005-01-01

    The solubility and hydrolysis of carbonyl sulfide in binary mixture of diethylene glycol diethyl ether and water are studied as a function of composition. The use of an aqueous solution of diethylene glycol diethyl ether enhances the solubility and hydrolysis rate of carbonyl sulfide compared with that in pure water. The composition of the mixture with maximum hydrolysis rate varies with temperature. The thermophysical properties including density, viscosity, and surface tension as a function of composition at 20℃ under atmospheric pressure as well as liquid-liquid equilibrium (LLE) data over the temperature range from 28℃ to 90℃ are also measured for the binary mixture.

  2. Improvement on stability of square planar rhodium (Ⅰ) complexes for carbonylation of methanol to acetic acid

    Institute of Scientific and Technical Information of China (English)

    蒋华; 潘平来; 袁国卿; 陈新滋

    1999-01-01

    A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces the investment on the equipment.

  3. Photopromoted carbonylation of olefins with carbon dioxide and labelling studies with 13CO2 and 13CH3OH

    Institute of Scientific and Technical Information of China (English)

    YIN Jingmei; GAO Dabin; HU Jiehan; ZHOU Guangyun; JIA Yingping; WANG Xiangsheng

    2003-01-01

    Photopromoted carbonylation of olefins with carbon dioxide can be completed in ambient conditions (room temperatures and atmospheric pressure) by Co(OAc)2 catalysis. It was found that in carbonyl carbons of methyl ester of aliphatic acid 50% is from CO2 and the other 50% from CH3OH by labelling experimental with 13CO2 and 13CH3OH.

  4. Enhanced antioxidation and electromagnetic properties of Co-coated flaky carbonyl iron particles prepared by electroless plating

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yingying, E-mail: zyzlchappy1989@163.com [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); Zhou, Wancheng [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); Li, Rong [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China); No. 603 Faculty, Xi’an Institute of High Technology, Xi’an 710025 (China); Mu, Yang; Qing, Yuchang [State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, Shaanxi 710072 (China)

    2015-07-15

    Highlights: • Co-coated carbonyl iron particles were prepared by electroless plating method. • The obvious weight gain of carbonyl iron was deferred to 400 °C after Co-coated. • The permeability of the Co-coated particle composite kept almost invariable. • Co-coated carbonyl iron composite reserves a better absorption after heat treatment. - Abstract: Co was successfully coated on the surface of flaky carbonyl iron particles using an electroless plating method. The morphologies, composition, as well as magnetic, antioxidation and electromagnetic properties of the samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), vibrating sample magnetometer (VSM), thermogravimetric (TG) and microwave network analyzer. TG curve shows that the obvious weight gain of carbonyl iron was deferred from 300 to 400 °C after Co-coated. In contrast to raw carbonyl iron, the Co-coated carbonyl iron shows better stability on electromagnetic properties after 300 °C heat treatment for 10 h, demonstrating that the Co coating can act as the protection of carbonyl iron.

  5. Dormancy alleviation by NO or HCN leading to decline of protein carbonylation levels in apple (Malus domestica Borkh.) embryos.

    Science.gov (United States)

    Krasuska, Urszula; Ciacka, Katarzyna; Dębska, Karolina; Bogatek, Renata; Gniazdowska, Agnieszka

    2014-08-15

    Deep dormancy of apple (Malus domestica Borkh.) embryos can be overcome by short-term pre-treatment with nitric oxide (NO) or hydrogen cyanide (HCN). Dormancy alleviation of embryos modulated by NO or HCN and the first step of germination depend on temporary increased production of reactive oxygen species (ROS). Direct oxidative attack on some amino acid residues or secondary reactions via reactive carbohydrates and lipids can lead to the formation of protein carbonyl derivatives. Protein carbonylation is a widely accepted covalent and irreversible modification resulting in inhibition or alteration of enzyme/protein activities. It also increases the susceptibility of proteins to proteolytic degradation. The aim of this work was to investigate protein carbonylation in germinating apple embryos, the dormancy of which was removed by pre-treatment with NO or HCN donors. It was performed using a quantitative spectrophotometric method, while patterns of carbonylated protein in embryo axes were analyzed by immunochemical techniques. The highest concentration of protein carbonyl groups was observed in dormant embryos. It declined in germinating embryos pre-treated with NO or HCN, suggesting elevated degradation of modified proteins during seedling formation. A decrease in the concentration of carbonylated proteins was accompanied by modification in proteolytic activity in germinating apple embryos. A strict correlation between the level of protein carbonyl groups and cotyledon growth and greening was detected. Moreover, direct in vitro carbonylation of BSA treated with NO or HCN donors was analyzed, showing action of both signaling molecules as protein oxidation agents.

  6. Green Synthesis and Regioselective Control of Sn/I2 Mediated Allylation of Carbonyl Compounds with Crotyl Halide in Water

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yan; ZHA,Zhang-Gen; ZHOU,Yu-Qing; WANG,Zhi-Yong

    2004-01-01

    @@ Barbier-type carbonyl allylation is particularly useful due to ease of operation and the availability and tractability of allylic substrates,[1] Metals such as indium, zinc and tin are often used as the mediator. Here we present a green approach toward the synthesis, that is, Sn/I2 mediated allylation of carbonyl compounds with crotyl halide in water.

  7. Mitochondrial ATP synthase is a target for TNBS-induced protein carbonylation in XS-106 dendritic cells.

    Science.gov (United States)

    Je, Jeong Hwan; Lee, Tae Hyung; Kim, Dong Hyun; Cho, Young Hun; Lee, Ju Hee; Kim, Soo Chan; Lee, Sang-Kyou; Lee, Jaewon; Lee, Min-Geol

    2008-06-01

    ROS are produced in dendritic cells (DCs) during antigen presentation in contact hypersensitivity (CHS). As a result, ROS cause a number of nonenzymatic protein modifications, including carbonylation, which is the most widely used marker of oxidative stress. 2,4,6-Trinitrobenzene sulfonic acid (TNBS) is a well-characterized contact allergen that results in the formation of ROS. However, proteins that are carbonylated in DCs in response to TNBS have not been identified. To study ROS-dependent protein carbonylation in response to TNBS, we used the well-established mouse DC line, XS-106. We focused on the effects of TNBS on oxidation by examining selected oxidative markers. We identified TNBS-induced ROS and myeloperoxidase (MPO) proteins and demonstrated that the increase in ROS resulted in IL-12 production. The increase in oxidation was further confirmed by an oxidation-dependent increase in protein modifications, such as carbonylation. In fact, TNBS strongly induced carbonylation of mitochondrial adenosine triphosphate (ATP) synthase in XS-106 DCs, as determined by MALDI-TOF analysis and 2-D Western blotting. ROS production and protein carbonylation were confirmed in human monocyte-derived DCs (Mo-DCs). Furthermore, glutathione (GSH) decreased ROS and protein carbonylation in Mo-DCs. Carbonylation of ATP synthase in DCs may contribute to the pathophysiology of CHS.

  8. Regiospecific oxidation of an alkyl group of aromatic amine to carbonyl group by DDQ in aq.medium

    Institute of Scientific and Technical Information of China (English)

    Madhav S. Mane; Ravi S. Balaskar; Sandip N. Gavade; Pramod N. Pabrekar; Murlidhar S. Shingare; Dhananjay V. Mane

    2011-01-01

    The regiospecific oxidation of alkyl group of both sterically hindered and unhindered aromatic amine to corresponding carbonyl compound was done in aq. medium by using DDQ. The optimized reaction protocol was found to be most simple, high yielding and novel method for oxidation of alkyl group of aromatic amine in to its carbonyl compound.

  9. Synthesis of the [beta]-D-glucosyl ester of [carbonyl-[sup 13]C]-indole-3-acetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Jakas, A.; Magnus, V. (Rudjer Boskovic Inst., Zagreb (Croatia)); Horvat, S.; Sandberg, G. (Swedish Univ. of Agricultural Sciences, Uppsala (Sweden))

    1993-10-01

    An efficient, operationally simple synthetic approach to 1-O-([carbonyl-[sup 13]C]-indole-3'-ylacetyl)-[beta]-D-glucopyranose is described. The synthesis was carried out by fusing a fully benzylated 1-O-glucosylpseudourea intermediate with [carbonyl-[sup 13]C]-indole-3-acetic acid, followed by hydrogenolytic removal of the protective groups. (Author).

  10. Efficient preparation of carbamates by Rh-catalysed oxidative carbonylation: unveiling the role of the oxidant.

    Science.gov (United States)

    Iturmendi, Amaia; Iglesias, Manuel; Munárriz, Julen; Polo, Victor; Pérez-Torrente, Jesús J; Oro, Luis A

    2016-12-22

    The synthesis of a wide variety of carbamates from amines, alcohols and carbon monoxide has been achieved by means of a Rh-catalysed oxidative carbonylation reaction that uses Oxone as a stoichiometric oxidant. In-depth studies on the reaction mechanism shed light on the intimate role of Oxone in the catalytic cycle.

  11. Weak carbonyl-methyl intermolecular interactions in acetone clusters explored by IR plus VUV spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Guan, Jiwen [MOE Key Laboratory of Laser Life Science and Institute of Laser Life Science, College of Biophotonics, South China Normal University, Guangzhou 510631 (China); Hu, Yongjun, E-mail: yjhu@scnu.edu.cn [MOE Key Laboratory of Laser Life Science and Institute of Laser Life Science, College of Biophotonics, South China Normal University, Guangzhou 510631 (China); Xie, Min [MOE Key Laboratory of Laser Life Science and Institute of Laser Life Science, College of Biophotonics, South China Normal University, Guangzhou 510631 (China); Bernstein, Elliot R. [Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872 (United States)

    2012-09-11

    Highlights: Black-Right-Pointing-Pointer The carbonyl overtone of acetone clusters is observed by IR-VUV spectroscopy. Black-Right-Pointing-Pointer Acetone molecules in the dimer are stacked with an antiparallel way. Black-Right-Pointing-Pointer The structure of the acetone trimer and the tetramer are the cyclic structures. Black-Right-Pointing-Pointer The carbonyl groups would interact with the methyl groups in acetone clusters. Black-Right-Pointing-Pointer These weak interactions are further confirmed by H/D substitution experiment. -- Abstract: Size-selected IR-VUV spectroscopy is employed to detect vibrational characteristics in the region 2850 {approx} 3550 cm{sup -1} of neutral acetone and its clusters (CH{sub 3}COCH{sub 3}){sub n} (n = 1-4). Features around 3440 cm{sup -1} in the spectra of acetone monomer and its clusters are assigned to the carbonyl stretch (CO) overtone. These features red-shift from 3455 to 3433 cm{sup -1} as the size of the clusters increases from the monomer to the tetramer. Based on calculations, the experimental IR spectra in the C=O overtone region suggest that the dominant structures for the acetone trimer and tetramer should be cyclic in the supersonic expansion sample. This study also suggests that the carbonyl groups interact with the methyl groups in the acetone clusters. These weak interactions are further confirmed by the use of deuterium substitution.

  12. Palladium-Catalyzed Carbonylation of Primary Amines in Supercritical Carbon Dioxide

    Institute of Scientific and Technical Information of China (English)

    李金恒; 江焕峰; 陈鸣才

    2001-01-01

    The chemoselectity of the palladimm-catalyzed carbonylation of amines was affected by the addition of MeOH in supercritical carbon dioxide. The results show different selectivity in supercritical carbon dioxide CO2(sc) from that in alcohol.Methyl carbamate and its derivatives were obtained in high yields in CO2(sc).

  13. N-Heterocyclic Carbene-Palladium Complex Catalyzed Oxidative Carbonylation of Amines to Ureas

    Institute of Scientific and Technical Information of China (English)

    ZHENG,Shu-Zhan; PENG,Xin-Gao; LIU,Jian-Ming; SUN,Wei; XIA,Chun-Gu

    2007-01-01

    Palladium carbene shows high efficiency without any promoter on oxidative carbonylation of amines to ureas and a new type of palladium carbene complex containing both an aniline and an NHC ligands was found to be the active species for the reaction.

  14. Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

    Science.gov (United States)

    One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

  15. The carbonylation of phenyl bromide and its derivatives under visible light irradiation

    Institute of Scientific and Technical Information of China (English)

    Wen Hui Zhong; Ying Na Cui; Shen Min Li; Ying Ping Jia; Jing Mei Yin

    2012-01-01

    The carbonylation of phenyl bromide catalyzed by Co(OAc)2 has been investigated with PhCOPh as a sensitizer under visible light in the presence of basic additive.With strong base CH3ONa,PhCOOCH3 is produced in 70% yield with 100% selectivity,the similar results are also obtained with a stronger base (CH3)3CONa.However,with another strong base NaOH,the yield of the ester is only 40%.On the other hand,with weak base NaOAc or (n-C4Hg)3N,phenyl bromide cannot be carbonylated.The results of carbonylation of the six substituted phenyl bromides suggest that the activities of o,m,p-BrC6H4CH3 are similar to phenyl bromide,while the activities of o,m,p-BrC6H4Cl are higher with the high yields (≥93%) of the corresponding chloro-esters.In addition,the relative position of bromine and chlorine or methyl on phenyl ring has little effect on the activity of the carbonylation.

  16. α-Carbonyl Radical Cyclization for the Total Synthesis of Natural Products

    Institute of Scientific and Technical Information of China (English)

    SHA Chin-Kang; CHIU Rei-Torng; LIH Shinn-Horng; SANTHOSH K. C.; CHANG Ching-Jung; TSENG Wei-Hong; HO Wen-Yueh

    2003-01-01

    @@ Intramolecular radical cyclization reactions are now used routinely to synthesize carbocyclic and heterocyclicstructures. We have reported that α-carbonyl radicals 1, generated from the corresponding iodo ketones or enones,underwent intramolecular radical cyclization smoothly to afford products 2. [1,2

  17. Oxalyl chloride as a practical carbon monoxide source for carbonylation reactions

    DEFF Research Database (Denmark)

    Hansen, Steffen V F; Ulven, Trond

    2015-01-01

    A method for generation of high-quality carbon monoxide by decomposition of oxalyl chloride in an aqueous hydroxide solution is described. The usefulness of the method is demonstrated in the synthesis of heterocycles and for hydroxy-, alkoxy-, amino-, and reductive carbonylation reactions, in sev...

  18. Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, Burcin

    2015-01-01

    Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated ...

  19. Peculiar features of composition of carbonyl components of surface lipids in aquatic plants

    OpenAIRE

    І. О. Alexeevs’ka; V. M. Shepelenko; N. I. Shtemenko

    2006-01-01

    Carbonyl components content of aquatic plants’ surface lipids has been studied. High concentration of oxo-compounds in surface lipids of aquatic plants has been shown. It could reach 60 % of total value. Sufficient heterogeneity of surface lipids has been demonstrated. Unsaturated character of oxo-components in aquatic plants’ surface lipids has been assumed in the present work.

  20. Determination of protein carbonyls in plasma, cell extracts, tissue homogenates, isolated proteins

    DEFF Research Database (Denmark)

    Weber, Daniela; Davies, Michael J.; Grune, Tilman

    2015-01-01

    Protein oxidation is involved in regulatory physiological events as well as in damage to tissues and is thought to play a key role in the pathophysiology of diseases and in the aging process. Protein-bound carbonyls represent a marker of global protein oxidation, as they are generated by multiple...

  1. Preparation and characterization of carbonyl iron/glass composite absorber as matched load for isolator

    Science.gov (United States)

    Feng, Yongbao; Li, Yujiao; Qiu, Tai

    2012-09-01

    Composite absorbers made from 66 wt% carbonyl iron and 34 wt% low melting point glass powder were prepared by a pressureless sintering technique in a nitrogen atmosphere. Apparent porosity and bending strength of the as-prepared composites were investigated. The microstructure, heat resisting properties and electromagnetic properties were characterized by scanning electron microscopy, thermal gravimetric analysis-differential scanning calorimetry and vector network analyzer. The results show that the carbonyl iron/glass composite absorbers were difficult to densify. As the sintering temperature and soaking time increased, the apparent porosity first decreased and then increased, whereas the bending strength showed the opposite change. The composite absorber sintered at 520 °C for 40 min achieved the minimum apparent porosity of 13.08% and the highest bending strength of 52 MPa. Compared to the carbonyl iron/silicone rubber absorber, the carbonyl iron/glass composite absorber exhibited better heat resisting properties, and the initial oxidation temperature was increased about 200 °C. The composite absorber with a thickness of 1.25 mm showed a good microwave absorbing property in 8-12 GHz.

  2. Proteomic and carbonylation profile analysis of rat skeletal muscles following acute swimming exercise.

    Directory of Open Access Journals (Sweden)

    Francesca Magherini

    Full Text Available Previous studies by us and other groups characterized protein expression variation following long-term moderate training, whereas the effects of single bursts of exercise are less known. Making use of a proteomic approach, we investigated the effects of acute swimming exercise (ASE on protein expression and carbonylation patterns in two hind limb muscles: the Extensor Digitorum Longus (EDL and the Soleus, mostly composed of fast-twitch and slow-twitch fibres, respectively. Carbonylation is one of the most common oxidative modifications of proteins and a marker of oxidative stress. In fact, several studies suggest that physical activity and the consequent increase in oxygen consumption can lead to increase in reactive oxygen and nitrogen species (RONS production, hence the interest in examining the impact of RONS on skeletal muscle proteins following ASE. Results indicate that protein expression is unaffected by ASE in both muscle types. Unexpectedly, the protein carbonylation level was reduced following ASE. In particular, the analysis found 31 and 5 spots, in Soleus and EDL muscles respectively, whose carbonylation is reduced after ASE. Lipid peroxidation levels in Soleus were markedly reduced as well. Most of the decarbonylated proteins are involved either in the regulation of muscle contractions or in the regulation of energy metabolism. A number of hypotheses may be advanced to account for such results, which will be addressed in future studies.

  3. Inactivation of cellular enzymes by carbonyls and protein-bound glycation/glycoxidation products

    DEFF Research Database (Denmark)

    Morgan, Philip E; Dean, Roger T; Davies, Michael Jonathan

    2002-01-01

    Diabetic plasma contains elevated levels of glucose and various low-molecular-weight carbonyl compounds derived from the metabolism of glucose and related materials. These compounds react with protein side chains (Arg, Lys, Cys, and His) to give glycated materials and advanced glycation end produ...

  4. Reductive Deoxygenation of Carbonyl to Methylene by LiAlH4/InBr3

    Institute of Scientific and Technical Information of China (English)

    Nan Yan FU; Xue Mei ZHAO; Yao Feng YUAN; Ji Tao WANG

    2003-01-01

    The reductive deoxygenation of aldehydes and ketones into the corresponding alkanes isaccomplished by LiA1H4 in the presence of Lewis acid InBr3. It provides a convenient method tocomplete the transformation from carbonyl compounds to alkanes.

  5. Synthesis, spectroscopic characterizations, crystal structures and DFT studies of nalidixic acid carbonyl hydrazones derivatives

    Science.gov (United States)

    Bergamini, F. R. G.; Ribeiro, M. A.; Lancellotti, M.; Machado, D.; Miranda, P. C. M. L.; Cuin, A.; Formiga, A. L. B.; Corbi, P. P.

    2016-09-01

    This article describes the synthesis and characterization of the 1-ethyl-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazide (hzd) and six carbonyl hydrazones derivatives of the nalidixic with 1H-pyrrol-2-ylmethylidene (hpyrr), 1H-imidazol-2-ylmethylidene (h2imi), pyridin-2-ylmethylidene (h2py), pyridin-3-ylmethylidene (h3py), pyridin-4-ylmethylidene(h4py) and (2-hydroxyphenyl)methylidene (hsali). The carbonyl hydrazones were characterized by elemental and ESI-QTOF-MS analyses, IR and detailed NMR spectroscopic measurements. The 2D NMR experiments allowed the unambiguous assignment of the hydrogen, carbon and nitrogen atoms, which have not been reported for nalidixic acid carbonyl hydrazone derivatives so far. Crystal structures of hzd and the new carbonyl hydrazones h2imi, hpyrr and h3py were determined by X-ray diffraction studies. Although the synthesis of hzd was reported decades ago, the hzd crystal structure have not been reported yet. Geometric optimizations of all the characterized structures were performed with the aid of DFT studies. Despite the fact that the hydrazones with 2-pyridine carboxylic acid (h2py) and salicyl aldehyde (hsali) were already reported by literature, a detailed spectroscopic study followed by DFT studies are also reported for such compounds in this manuscript. Antimicrobial studies of the compounds are also presented.

  6. Levels, sources and health risks of carbonyls and BTEX in the ambient air of Beijing, China

    Institute of Scientific and Technical Information of China (English)

    Yujie Zhang; Yujing Mu; Junfeng Liu; Abdelwahid Mellouki

    2012-01-01

    The atmospheric concentrations of carbonyls and BTEX (benzene,toluene,ethylbenzene,m,p-xylene and o-xylene) were measured simultaneously at a same sampling site in Beijing from September 2008 to August 2010.The average concentrations of the total measured carbonyls during autumn,winter,spring,and summer were 37.7,31.3,39.7,50.5 μg/m3,respectively,and maximal values for their diurnal variations usually happened at noontime.In contrast to carbonyls,the average concentrations of the total measured BTEX during the four seasons were 27.2,31.9,23.2,19.1 μg/m3,respectively,and minimal values for their diurnal variations always occurred in the early afternoon.The average concentration for carbonyls increased about 24% from September 2008-August 2009 to September 2009-August 2010,for BTEX,increased about 15%.Integrated life time cancer risks for three carcinogens (benzene,formaldehyde and acetaldehyde) in Beijing exceeded the value of 1E-06,and the hazard quotient (HQ) of non-cancer risk of exposure to formaldehyde exceeded unity.

  7. The Solvent Mixture Sensitivity of Carbonyl Stretching Frequencies of 2-Pyrrolidinones and Related Compounds

    NARCIS (Netherlands)

    Perjessy, A.; Engberts, J.B.F.N.; Blandamer, M.J.

    1995-01-01

    The carbonyl stretching frequencies of 1-substituted 2-pyrrolidinones and related compounds were measured in binary mixtures of hexane-CDCl3 and acetonitrile-D2O and plotted against the mole fraction of the less polar co-solvent The v(C=O) vs. mole fraction correlations enabled to recognize and assi

  8. Direct photolysis of carbonyl compounds dissolved in cloud and fog~droplets

    Science.gov (United States)

    Epstein, S. A.; Tapavicza, E.; Furche, F.; Nizkorodov, S. A.

    2013-09-01

    Gas-phase photolysis is an important tropospheric sink for many carbonyl compounds; however the significance of direct photolysis of these compounds dissolved in cloud and fog droplets is uncertain. We develop a theoretical approach to assess the importance of aqueous photolysis for a series of carbonyls that possess carboxyl and hydroxyl functional groups by comparison with rates of other atmospheric processes. We use computationally and experimentally derived effective Henry's law constants, hydration equilibrium parameters, aqueous hydroxyl radical (OH) rate constants, and optical extinction coefficients to identify types of compounds that will (or will not) have competitive aqueous photolysis rates. We also present molecular dynamics simulations designed to estimate gas- and aqueous-phase extinction coefficients of unstudied atmospherically relevant compounds found in d-limonene and isoprene secondary organic aerosol. In addition, experiments designed to measure the photolysis rate of glyceraldehyde, an atmospherically relevant water-soluble organic compound, reveal that aqueous quantum yields are highly molecule-specific and cannot be extrapolated from measurements of structurally similar compounds. We find that only two out of the 92 carbonyl compounds investigated, pyruvic acid and acetoacetic acid, may have aqueous photolysis rates that exceed the rate of oxidation by dissolved OH. For almost all carbonyl compounds lacking α,β-conjugation that were investigated, atmospheric removal by direct photolysis in cloud and fog droplets can be neglected under typical atmospheric conditions.

  9. Study on the Carbonyl Iron Powder Based Nano-Composite Radar Wave Absorbing Coatings

    Institute of Scientific and Technical Information of China (English)

    HUANG Dong-zhen; WANG Zhi-hui; LV Yan-hong; HU Chuan-xin; LI Wan-zhi; LIANG wen-ting; YAO Jun-min

    2004-01-01

    With the rapid development of stealth technique, carbonyl iron powder is regarded as an ideal radar absorbing material. In this paper, radar absorbing properties of carbonyl iron powder was investigated by using nano composite and macroscopic multi- layer composite approach. The machine- chemistry composite methods were employed during the experiment to produce nano composite absorbent. Two carbonyl iron powders named HP1, HP2 and nano powder named HP3 were employed. Absorbents were obtained by adding 10% HP3 powder with average size of 28 nm to the HP1 and HP2 carbonyl iron powders by weight respectively. By a series of composite techniques, sample plate with the radar absorbing coating was prepared. Compared with the single coating, the wave absorbing properties were significantly improved. The working band in which the wave reflectivity was less than 5 db was 4.8 ~ 18 GHz with the coating thickness of 1.0 mm. The lowest reflectivity was found to be 12.34 db at 8 GHz. The wave absorbing coating with thin thickness,broadband and strong absorbing properties was obtained.

  10. Chemo- and Stereoselective Reduction of Polyfunctional Carbonyl Compounds by Mucor rouxii

    Directory of Open Access Journals (Sweden)

    Constanza P. Mangone

    2000-03-01

    Full Text Available Several polyfunctional carbonyl compounds, such as α- and β-ketoesters, were chemo- and stereoselectively reduced by Mucor rouxii cultures in water and in organic solvents. Results show that reductions can be carried out in a variety of organic solvents.

  11. NEAR-CONTINUOUS MEASUREMENT OF HYDROGEN SULFIDE AND CARBONYL SULFIDE BY AN AUTOMATIC GAS CHROMATOGRAPH

    Science.gov (United States)

    An automatic gas chromatograph with a flame photometric detector that samples and analyzes hydrogen sulfide and carbonyl sulfide at 30-s intervals is described. Temperature programming was used to elute trace amounts of carbon disulfide present in each injection from a Supelpak-S...

  12. NMR Studies of Structure-Reactivity Relationships in Carbonyl Reduction: A Collaborative Advanced Laboratory Experiment

    Science.gov (United States)

    Marincean, Simona; Smith, Sheila R.; Fritz, Michael; Lee, Byung Joo; Rizk, Zeinab

    2012-01-01

    An upper-division laboratory project has been developed as a collaborative investigation of a reaction routinely taught in organic chemistry courses: the reduction of carbonyl compounds by borohydride reagents. Determination of several trends regarding structure-activity relationship was possible because each student contributed his or her results…

  13. Hydration and hydrogen bonding of carbonyls in dimyristoyl-phosphatidylcholine bilayer.

    Science.gov (United States)

    Volkov, Victor V; Nuti, Francesca; Takaoka, Yuji; Chelli, Riccardo; Papini, Anna Maria; Righini, Roberto

    2006-07-26

    We combine two-color ultrafast infrared spectroscopy and molecular dynamics simulation to investigate the hydration of carbonyl moieties in a dimyristoyl-phosphatidylcholine bilayer. Excitation with femtosecond infrared pulses of the OD stretching mode of heavy water produces a time dependent change of the absorption band of the phospholipid carbonyl groups. This intermolecular vibrational coupling affects the entire C=O band, thus suggesting that the optical inhomogeneity of the infrared response of carbonyl in phospholipid membranes cannot be attributed to the variance in hydration. Both the experimental and the theoretical results demonstrate that sn-1 carbonyl has a higher propensity to form hydrogen bonds with water in comparison to sn-2. The time-resolved experiment allows following the evolution of the system from a nonequilibrium localization of energy in the OD stretching mode to a thermally equilibrated condition and provides the characteristic time constants of the process. The approach opens a new opportunity for investigation of intermolecular structural relations in complex systems, like membranes, polymers, proteins, and glasses.

  14. Ketene as a Reaction Intermediate in the Carbonylation of Dimethyl Ether to Methyl Acetate over Mordenite

    DEFF Research Database (Denmark)

    Rasmussen, Dominik Bjørn; Christensen, Jakob Munkholt; Temel, Burcin;

    2015-01-01

    Unprecedented insight into the carbonylation of dimethyl ether over Mordenite is provided through the identification of ketene (CH2CO) as a reaction intermediate. The formation of ketene is predicted by detailed DFT calculations and verified experimentally by the observation of doubly deuterated...

  15. [pi] Backbonding in Carbonyl Complexes and Carbon-Oxygen Stretching Frequencies: A Molecular Modeling Exercise

    Science.gov (United States)

    Montgomery, Craig D.

    2007-01-01

    An exercise is described that has illustrated the effect of various factors on [pi] backbonding to carbonyl ligands, where the students can view the molecular orbitals corresponding to the M-CO [pi] interaction as well as the competing interaction between the metal and co-ligands. The visual and hands-on nature of the modeling exercise has helped…

  16. Towards a General Understanding of Carbonyl-Stabilised Ammonium Ylide-Mediated Epoxidation Reactions.

    Science.gov (United States)

    Novacek, Johanna; Roiser, Lukas; Zielke, Katharina; Robiette, Raphaël; Waser, Mario

    2016-08-01

    The key factors for carbonyl-stabilised ammonium ylide-mediated epoxidation reactions were systematically investigated by experimental and computational means and the hereby obtained energy profiles provide explanations for the observed experimental results. In addition, we were able to identify the first tertiary amine-based chiral auxiliary that allows for high enantioselectivities and high yields for such epoxidation reactions.

  17. Modular Approach for Novel Nanostructered Polycondensates Enabled by the Unique Selectivity of Carbonyl Biscaprolactam

    NARCIS (Netherlands)

    Loontjens, Ton

    2003-01-01

    New enabling chemistries have been developed to produce novel well-defined polymeric materials through the additions of small amounts of reactive functional compounds to standard polymers during regular processing steps. We found that carbonyl biscaprolactam and its derivatives couple polymer chains

  18. Ab initio study on the mechanism of rhodium-complexcatalyzed carbonylation of methanol to acetic acid

    Institute of Scientific and Technical Information of China (English)

    LEI; Ming

    2001-01-01

    [1]Thomas, R., Cundari, T. R., Computational studies of transition metal-main group multiple bonding, Chem. Rev., 2000,100: 807.[2]Maricel Torrent, Miquel Sola, Gernot Frenking, Theoretical studies of some transition-metal-mediated reactions of industrial and synthetic importance, Chem. Rev., 2000, 100: 439.[3]Paulik, F. E., Roth, J. F., Catalysts for the low-pressure carbonylation of menthanol to acetic acid, Chem. Commun., 1968,24: 1578.[4]Jiang Hua, Diao Kaisheng, Pan Pinglai et al., A new class of rhodium complexes containing free donor atoms and their intramolecular substitution reaction, Chin. J. Chem., 2000, 18: 752.[5]Jiang Dazhi, Li Xiaobao, Wang Enlai, Synthesis Chemistry ofCarbonylation, Beijing: Chemical Technology Press, 1996.[6]Adamson, G. W., Daly, J. J., Forster, D., Reduction of iolocarbonyl rhodium ions with methyl iodide, structure of the rho-dium acetyl complex: [Me3PhN+], [Rh2I6-(Me(O)2(CO)2)]2-, J. Organomet. Chem., 1974, 71: C 17.[7]Forster, D., On the mechanism of a rhodium-complex-catalyzed carbonylation of methanol to acetic acid, J. Am. Chem.Soc., 1976, 98: 846.[8]Hjortkjaer, J., Jensen, O. R., Rhodium complexes catalyzed methanol carbonylation, Ind. Eng. Chem. Prod. Dev., 1976, 15:46.[9]Jeffrey, P., Wadt, W. R., Ab initio effective core potentials for molecular calculations, Potentials for the transition metalatoms Sc to Hg, J. Chem. Phys., 1995, 82: 270.[10]Frisch, M. J., Trunks, G. W., Schlegel, H. B. et al., Gaussian 94, Pittsburgh PA: Gaussian, Inc., 1995.[11]Lei Ming, Feng Wenlin, Xu Zhenfeng et al., A theoretical study on the key reactions of hydroformylation cycle by modi-fied carbonyl cobalt, Chemical Journal of Chinese University, 2001, 22: 455.[12]Lei Ming, Feng Wenlin, Xu Zhenfeng, Ab initio MO study on the reaction mechanism for carbonyl insertion catalyzed by the carbonyl cobalt complex, Chemical Research in Chinese University, 2000, 19:31.

  19. Proteomic identification of carbonylated proteins in F344 rat hippocampus after 1-bromopropane exposure.

    Science.gov (United States)

    Huang, Zhenlie; Ichihara, Sahoko; Oikawa, Shinji; Chang, Jie; Zhang, Lingyi; Subramanian, Kaviarasan; Mohideen, Sahabudeen Sheik; Ichihara, Gaku

    2012-08-15

    1-Bromopropane (1-BP) is neurotoxic in both experimental animals and humans. Previous proteomic analysis of rat hippocampus implicated alteration of protein expression in oxidative stress, suggesting that oxidative stress plays a role in 1-BP-induced neurotoxicity. To understand this role at the protein level, we exposed male F344 rats to 1-BP at 0, 400, or 1000 ppm for 8h/day for 1 week or 4 weeks by inhalation and quantitated changes in hippocampal protein carbonyl using a protein carbonyl assay, two-dimensional gel electrophoresis (2-DE), immunoblotting, and matrix-assisted laser-desorption ionization time-of-flight mass spectrometry (MALDI-TOF-TOF/MS). Hippocampal reactive oxygen species and protein carbonyl were significantly increased, demonstrating 1-BP-associated induction of oxidative stress and protein damage. MALDI-TOF-TOF/MS identified 10 individual proteins with increased carbonyl modification (p < 0.05; fold-change ≥ 1.5). The identified proteins were involved in diverse biological processes including glycolysis, ATP production, tyrosine catabolism, GTP binding, guanine degradation, and neuronal metabolism of dopamine. Hippocampal triosephosphate isomerase (TPI) activity was significantly reduced and negatively correlated with TPI carbonylation (p < 0.001; r = 0.83). Advanced glycation end-product (AGE) levels were significantly elevated both in the hippocampus and plasma, and hippocampal AGEs correlated negatively with TPI activity (p < 0.001; r = 0.71). In conclusion, 1-BP-induced neurotoxicity in the rat hippocampus seems to involve oxidative damage of cellular proteins, decreased TPI activity, and elevated AGEs.

  20. Spatial distributions of airborne di-carbonyls in urban and rural areas in China

    Science.gov (United States)

    Lui, K. H.; Dai, Wen-Ting; Chan, C. S.; Ho, Steven Sai Hang; Cao, Jun-Ji; Lee, S. C.; Ho, K. F.

    2017-04-01

    Gaseous glyoxal and methylglyoxal concentrations were characterized in nine cities of China during 2010-2011. The average summer (winter) glyoxal and methylglyoxal concentrations were 36.4-178.4 (12.3-241.4) and 67.8-359.4 (28.4-530.0) ng/m3, respectively. In summer, the highest average glyoxal concentration was in Guangzhou (GZ), while the lowest was in Shanghai (SH). In winter, Xiamen (XM) showed the highest average methylglyoxal concentration and Yantai (YT) reported the lowest. Both di-carbonyls showed distinct seasonal variations. The maximum average methylglyoxal concentration was approximately twice as much as glyoxal, which is consistent with the results of other studies. Glyoxal-to-methylglyoxal ratios showed that there was a consistent direct source of emissions in remote areas such as Qinghai Lake and Lhasa in both seasons (r ≥ 0.9). Pearson's correlation analysis suggested possible similar sources formation (R ≥ 0.7) for the two di-carbonyls in winter. Multiple linear regression analyses demonstrated that every 1 °C temperature increase could lead to a > 2% increase in the concentration of the di-carbonyls in both seasons. There was a greater percentage gain for glyoxal in winter than in summer for the same temperature increase. The northeast monsoon occurs in winter, and for every 1 ms- 1 increase in wind speed, > 20% of the di-carbonyls can be transferred out of China. This study is useful to understand about the secondary organic aerosol formation in the areas, the statistical analysis can provide information about the relationships between these carbonyls in atmosphere.

  1. Design and fabrication of microfluidic mixer from carbonyl iron–PDMS composite membrane

    KAUST Repository

    Li, Jiaxing

    2010-10-12

    This paper introduces a carbonyl iron-PDMS (CI-PDMS) composite magnetic elastomer in which carbonyl iron (CI) particles are uniformly distributed in a PDMS matrix. The CI particles and the PDMS were mixed at different weight ratios and tested to determine the influence of CI concentration. The magnetic and mechanical properties of the magnetic elastomers were characterized, respectively, by vibrating-sample magnetometer and by tensile testing using a mechanical analyzer. The elastomer was found to exhibit high magnetization and good mechanical flexibility. The morphology and deformation of the CI-PDMS membrane also were observed. A magnetically actuated microfluidic mixer (that is, a micromixer) integrated with CI-PDMS elastomer membranes was successfully designed and fabricated. The high efficiency and quality of the mixing makes possible the impressive potential applications of this unique CI-PDMS material in microfluidic systems. © Springer-Verlag 2010.

  2. The N-heterocyclic carbene chemistry of transition-metal carbonyl clusters.

    Science.gov (United States)

    Cabeza, Javier A; García-Álvarez, Pablo

    2011-11-01

    In the last decade, chemists have dedicated many efforts to investigate the coordination chemistry of N-heterocyclic carbenes (NHCs). Although most of that research activity has been devoted to mononuclear complexes, transition-metal carbonyl clusters have not escaped from these investigations. This critical review, which is focussed on the reactivity of NHCs (or their precursors) with transition-metal carbonyl clusters (mostly are of ruthenium and osmium) and on the transformations underwent by the NHC-containing species initially formed in those reactions, shows that the polynuclear character of these metallic compounds or, more precisely, the close proximity of one or more metal atoms to that which is or can be attached to the NHC ligand, is responsible for reactivity patterns that have no parallel in the NHC chemistry of mononuclear complexes (74 references).

  3. The kinetics and mechanism of dissociation of metal carbonyls in high infrared laser fields

    Science.gov (United States)

    Langsam, Y.; Ronn, A. M.

    1981-01-01

    The method of laser induced dielectric breakdown has been used to study the dissociation of three metal carbonyls. Following non-resonant excitation by a TEA CO 2 laser, amorphous micro-metallic particles are deposited. The identity of the various species within a laser induced plasma for a series of related reactant molecules, has been determined using infrared and visible real time fluorescence techniques. Based upon the energetics of dissociation and the relative magnitudes of the rates of activation and deactivation for various collision partners of the plasma fluorescence, an energy transfer map as well as probable mechanisms are proposed. The kinetics of a variety of chemical reactions under plasma conditions are discussed in terms of elementary collision theory. It is shown that the internal vibration manifold of the metal carbonyls is equilibrated prior to the dissociation in agreement with the majority of laser induced multiphoton dissociation experiments.

  4. A catalyst for the carbonylation of methanol to acetic acid in gaseous phase

    Institute of Scientific and Technical Information of China (English)

    潘平来; 柳忠阳; 朱长城; 袁国卿

    1996-01-01

    A novel Rh/Ys catalyst for the carbonylation of methanol to acetic acid in gaseous phase is reported. The porous carbon beads (Ys) prepared from the carbonation of poly(vinylidene chloride) were used as the support. This catalyst has a specific surface area of 1 000 m2/g, high mechanical strength and thermal stability. The average diameter of the pore is in the range of 0.8 - 1.2nm. Experimental evidence showed that this catalyst was of high activity and selectivity, which could compare to those of the homogeneous catalyst from Monsanto. The catalytic rate could get to 900 g AcOH/g Rh·h during the carbonylation of methanol to acetic acid. The fine spreading of Ph over the Ys surface is the key factor for the activity.

  5. Impact of lipid content and composition on lipid oxidation and protein carbonylation in experimental fermented sausages.

    Science.gov (United States)

    Fuentes, Verónica; Estévez, Mario; Ventanas, Jesús; Ventanas, Sonia

    2014-03-15

    This study aims to investigate the effect of lipid content (∼4%, ∼10% and ∼15%) and composition (different lipid sources; animal fat and sunflower oil) on the oxidative stability of proteins and lipids in experimental fermented sausages. Increasing the lipid content of sausages enhanced the susceptibility of lipids to oxidation whereas the effect on the formation of specific carbonyls from protein oxidation was not so evident. Sausages manufactured with different lipid sources affected the susceptibility of lipids and proteins to oxidation as a likely result of the modifications in the fatty acid profile, as well as to the presence of antioxidant compounds. While the fatty acid profile had a major effect on the occurrence and extent of lipid oxidation, the presence of compounds with potential antioxidant activity may be more influential on the extent of protein carbonylation.

  6. Rheological properties of magnetorheological fluid prepared by gelatin-carbonyl iron composite particles

    Institute of Scientific and Technical Information of China (English)

    PAN Hua-jin; HUANG Hong-jun; ZHANG Ling-zhen; QI Jian-ying; CAO Shao-kun

    2005-01-01

    Gelatin-carbonyl iron composite particle was prepared by micro emulsion method. The analysis of scanning electron microscope(SEM) shows that the ultrafine particles are spheroids coated by gelatin, and the average sizes of particles are 3-10 μm. The specific saturation magnetization σs is 130.9 A·m2/kg, coercivity Hc is 0.823 A/m, and residual magnetism r is 4.98 Am2/kg for the composite particles. It is shown that the particles possess properties of soft magnetic. The yield stress of magnetorheological fluid(MRF) with composite particle reaches 70 kPa at 0.5 T magnetic induction. Magnetorheological effects are superior in lower magnetic field intensity and the subsidence stability of the MRF is excellent compared with pure carbonyl iron powder.

  7. Microfluidic lab-on-a-chip derivatization for gaseous carbonyl analysis.

    Science.gov (United States)

    Pang, Xiaobing; Lewis, Alastair C; Ródenas-García, Milagros

    2013-06-28

    We present a microfluidic lab-on-a-chip derivatization technique for the analysis of gaseous carbonyl compounds using O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) as the derivatizing reagent. The novel microfluidic lab-on-a-chip derivatization technique has been developed to measure nmol per mole (ppbv) mixing ratios of gaseous carbonyl compounds, which are of particular importance to atmospheric chemistry. The technique utilised a planar glass microreactor comprising three inlets and one outlet, gas and fluid splitting and combining channels, mixing junctions, and a 2.0m long, 620μm internal diameter reaction microchannel. The microreactor integrated three functions, providing: (1) a gas and liquid mixer and reactor, (2) reagent heating, and (3) sample pre-concentration. The concentration of derivatization solution, the volumetric flow rates of the incoming gas sample and PFBHA solution, and the temperature of the microreactor were optimised to achieve a near real-time measurement. The enhanced phase contact area-to-volume ratio and the high heat transfer rate in the microreactor resulted in a fast and high efficiency derivatization reaction, generating an effluent stream which was ready for direct introduction to GC-MS. Good linearity was observed for eight carbonyl compounds over the measurement ranges of 1-500ppbv when they were derivatized under optimal reaction conditions. The method detection limits (MDLs) were below 0.10nmolmol(-1) for most carbonyls in this study, which is below or close to their typical concentrations in clean ambient air. The performance of the technique was assessed by applying the methodology to the quantification of glyoxal (GLY) and methylglyoxal (MGLY) formed during isoprene photo-oxidation in an outdoor photoreactor chamber (EUPHORE). Good agreements between GLY and MGLY measurements were obtained comparing this new technique with Fourier Transform InfraRed (FTIR), which provides support for the potential effectiveness of

  8. Influence of shape anisotropy on microwave complex permeability in carbonyl iron flakes/epoxy resin composites

    Institute of Scientific and Technical Information of China (English)

    Wen Fu-Sheng; Qiao Liang; Zhou Dong; Zuo Wen-Liang; Yi Hai-Bo; Li Fa-Shen

    2008-01-01

    To explore the mechanism of carbonyl iron flake composites for microwave complex permeability, this paper investigates the feature of the flakes. The shape anisotropy was certified by the results of the magnetization hysteresis loops and the Mossbauer spectra. Furthermore, the shape anisotropy was used to explain the origin of composite microwave performance, and the calculated results agree with the experiment. It is believed that the shape anisotropy dominates microwave complex permeability, and the natural resonance plays main role in flake.

  9. Carbonylative Heck Reactions Using CO Generated ex Situ in a Two-Chamber System

    DEFF Research Database (Denmark)

    Hermange, Philippe; Gøgsig, Thomas; Lindhardt, Anders Thyboe;

    2011-01-01

    A carbonylative Heck reaction of aryl iodides and styrene derivatives employing a two-chamber system using a stable, crystalline, and nontransition metal based carbon monoxide source is reported. By applying near-stoichiometric amounts of the carbon monoxide precursor, an effective exploitation o...... of the hazardous CO gas is obtained affording chalcone derivatives in good yields. Application to isotope labeling, incorporating 13CO, was further established....

  10. Coupling Reaction of Carbonyl Compounds Mediated by Gallium Metal in Aqueous Media

    Institute of Scientific and Technical Information of China (English)

    汪志勇; 袁仕祯; 查正根; 张祖德

    2003-01-01

    A simple and effective pinacol coupling of various aromatic aldehydes mediated by gallium in good yields has been carried out. The reaction is highly effective in water in the prurience of KOH or HCl and was strongly affected by the steric environ-ment surrounding the carbonyl group. Aliphaflc aldehydes, ke-tones and aromatic ketones appear inert under the same reac-tion conditions.

  11. Influence of carbonyl stress on rheological alterations of blood materials and decarbonylation effect of glutathione

    Institute of Scientific and Technical Information of China (English)

    彭密军; 蔡建光; 贺洪; 龚萍; 李国林; 汤婷; 朱泽瑞; 印大中

    2008-01-01

    The effects of various toxic carbonyls such as malondialdehyde(MDA),a secondary product of lipid peroxidation,and other aldehydes on rheological parameters and their relationship with aging-associated alterations were studied.Both MDA and glutaraldehyde(Glu) in different concentrations significantly increase viscosity,plastic viscosity and yield stress of human plasma and erythrocyte suspensions.MDA(20 mmol/L) reduces sharply the typical fluorescence of proteins(excitation 280 nm/emission 350 nm),and produces age pigment-like fluorescence with a strong emission peak at 460 nm when excites at 395 nm by only being incubated for some hours.In contrast,Glu decreases merely the fluorescence of proteins without producing age pigment-like fluorescence.These data suggest interestingly that the MDA-induced gradual protein cross linking seems to form from different mechanisms compared to the fast rheological changes of blood materials which may take place either in acute and chronic diseases or during aging.On the other hand,MDA induces various deleterious alterations of erythrocytes whereas glutathione(GSH) inhibits the MDA-related carbonyl stress in a concentration-dependent manner.The results indicate that carbonyl-amino reaction exists in the blood widely and GSH has the ability to interrupt or reverse this reaction in a certain way.It implies that carbonyl stress may be one of the important factors in blood stasis and suggests a theoretical and practical approach in anti-stresses and anti-aging.

  12. Formation of Small Gas Phase Carbonyls from Heterogeneous Oxidation of Polyunsaturated Fatty Acids (PUFA)

    Science.gov (United States)

    Zhou, S.; Zhao, R.; Lee, A.; Gao, S.; Abbatt, J.

    2011-12-01

    Fatty acids (FAs) are emitted into the atmosphere from gas and diesel powered vehicles, cooking, plants, and marine biota. Field measurements have suggested that FAs, including polyunsaturated fatty acids (PUFA), could make up an important contribution to the organic fraction of atmospheric aerosols. Due to the existence of carbon-carbon double bonds in their molecules, PUFA are believed to be highly reactive towards atmospheric oxidants such as OH and NO3 radicals and ozone, which will contribute to aerosol hygroscopicity and cloud condensation nuclei activity. Previous work from our group has shown that small carbonyls formed from the heterogeneous reaction of linoleic acid (LA) thin films with gas-phase O3. It is known that the formation of small carbonyls in the atmosphere is not only relevant to the atmospheric budget of volatile organic compounds but also to secondary organic aerosol formation. In the present study, using an online proton transfer reaction mass spectrometry (PTR-MS) and off-line gas chromatography-mass spectrometry (GC-MS) we again investigated carbonyl formation from the same reaction system, i.e. the heterogeneous ozonolysis of LA film. In addition to the previously reported carbonyls, malondialdehyde (MDA), a source of reactive oxygen species that is mutagenic, has been identified as a product for the first time. Small dicarbonyls, e.g. glyoxal, are expected to be formed from the further oxidation of MDA. In this presentation, the gas-phase chemistry of MDA with OH radicals using a newly built Teflon chamber in our group will also be presented.

  13. Characterization of Carbonyl Compounds in the Ambient Air of an Industrial City in Korea

    Directory of Open Access Journals (Sweden)

    Sung-Ok Baek

    2011-01-01

    Full Text Available The purpose of this study was to characterize spatial and temporal variations of carbonyl compounds in Gumi city, where a number of large electronic-industrial complexes are located. Carbonyl samples were collected at five sites in the Gumi area: three industrial, one commercial, and one residential area. Sampling was carried out throughout a year from December 2003 to November 2004. At one industrial site, samples were taken every six days, while those of the other sites were for seven consecutive days in every season. Each sample was collected for 150 minutes and at intervals of three times a day (morning, afternoon, and evening. A total of 476 samples were analyzed to determine 15 carbonyl compounds by the USEPA TO-11A (DNPH-cartridge/HPLC method. In general, acetaldehyde appeared to be the most abundant compound, followed by formaldehyde, and acetone+acrolein. Mean concentrations of acetaldehyde were two to three times higher in the industrial sites than in the other sites, with its maximum of 77.7 ppb. In contrast, ambient levels of formaldehyde did not show any significant difference between the industrial and non-industrial groups. Its concentrations peaked in summer probably due to the enhanced volatilization and photochemical reactivity. These results indicate significant emission sources of acetaldehyde in the Gumi industrial complexes. Mean concentrations of organic solvents (such as acetone+acrolein and methyl ethyl ketone were also significantly high in industrial areas. In conclusion, major sources of carbonyl compounds, including acetaldehyde, are strongly associated with industrial activities in the Gumi city area.

  14. The intramolecular charge transfer state in carbonyl-containing polyenes and carotenoids.

    Science.gov (United States)

    Enriquez, Miriam M; Fuciman, Marcel; LaFountain, Amy M; Wagner, Nicole L; Birge, Robert R; Frank, Harry A

    2010-09-30

    Numerous femtosecond time-resolved optical spectroscopic experiments have reported that the lifetime of the low-lying S(1) state of carbonyl-containing polyenes and carotenoids decreases with increasing solvent polarity. The effect becomes even more pronounced as the number of double bonds in the conjugated π-electron system decreases. The effect has been attributed to an intramolecular charge transfer (ICT) state coupled to S(1), but it is still not clear what the precise molecular nature of this state is, and how it is able to modulate the spectral and dynamic properties of polyenes and carotenoids. In this work, we examine the nature of the ICT state in three substituted polyenes: crocetindial, which contains two terminal, symmetrically substituted carbonyl groups in conjugation with the π-electron system, 8,8'-diapocarotene-8'-ol-8-al, which has one terminal conjugated carbonyl group and one hydroxyl group, and 8,8'-diapocarotene-8,8'-diol, which has two terminal, symmetrically positioned, hydroxyl groups but no carbonyls. Femtosecond time-resolved optical spectroscopic experiments on these molecules reveal that only the asymmetrically substituted 8,8'-diapocarotene-8'-ol-8-al exhibits any substantial effect of solvent on the excited state spectra and dynamics. The data are interpreted using molecular orbital theory which shows that the ICT state develops via mixing of the low-lying S(1) (2(1)A(g)-like) and S(2) (1(1)B(u)-like) excited singlet states to form a resultant state that preferentially evolves in polar solvent and exhibits a very large (∼25 D) dipole moment. Molecular dynamics calculations demonstrate that the features of the ICT state are present in ∼20 fs.

  15. Ionization of oriented carbonyl-sulfide molecules by intense circularly polarized laser pulses

    CERN Document Server

    Dimitrovski, Darko; Madsen, Lars Bojer; Filsinger, Frank; Meijer, Gerard; Küpper, Jochen; Holmegaard, Lotte; Kalhøj, Line; Nielsen, Jens H; Stapelfeldt, Henrik

    2010-01-01

    We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl-sulphide molecules by circularly-polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction of the molecular electric dipole moment. These findings are explained by a tunneling model invoking the laser-induced Stark shifts associated with the dipoles and polarizabilities of the molecule and its unrelaxed cation.

  16. Catalytic Addition of Simple Alkenes to Carbonyl Compounds Using Group 10 Metals.

    Science.gov (United States)

    Ho, Chun-Yu; Schleicher, Kristin D; Jamison, Timothy F

    2009-10-01

    Recent advances using nickel complexes in the activation of unactivated monosubstituted olefins for catalytic intermolecular carbon-carbon bond-forming reactions with carbonyl compounds, such as simple aldehydes, isocyanates, and conjugated aldehydes and ketones, are discussed. In these reactions, the olefins function as vinyl- and allylmetal equivalents, providing a new strategy for organic synthesis. Current limitations and the outlook for this new strategy are also discussed.

  17. Exchange of carbonyl sulfide (COS) between the atmosphere and various soils in China

    OpenAIRE

    Liu, J; C. Geng; Mu, Y; Zhang, Y; Wu, H

    2009-01-01

    Using a dynamic enclosure, the exchange fluxes of carbonyl sulfide (COS) between the atmosphere and 18 soils from 10 provinces in China were investigated. The emission or uptake of COS from the soils was highly dependent on the soil type, soil temperature, soil moisture, and atmospheric COS mixing ratio. In general, with the only exception being paddy soils, the soils in this investigation acted as sinks for atmospheric COS under wide ranges of soil temperature and soil moisture. Two i...

  18. Carbonyl sulfide exchange in soils for better estimates of ecosystem carbon uptake

    OpenAIRE

    M. E. Whelan; Hilton, T. W.; Berry, J. A.; M. Berkelhammer; A. R. Desai; Campbell, J. E.

    2015-01-01

    Carbonyl sulfide (COS) measurements are one of the emerging tools to better quantify gross primary production (GPP), the largest flux in the global carbon cycle. COS is a gas with a similar structure to CO2; COS uptake is thought to be a proxy for GPP. However, soils are a potential source or sink of COS. This study presents a framework for understanding soil-COS interactions. Excluding wetlands, most of the few observations of isolated soils that have been ...

  19. Sources and sinks of carbonyl sulfide in an agricultural field in the Southern Great Plains

    OpenAIRE

    Maseyk, Kadmiel; Berry, Joseph A; Billesbach, Dave; Campbell, John Elliott; Torn, Margaret S.; Zahniser, Mark; Seibt, Ulli

    2014-01-01

    Net photosynthesis is the largest single flux in the global carbon cycle, but controls over its variability are poorly understood because there is no direct way of measuring it at the ecosystem scale. We report observations of ecosystem carbonyl sulfide (COS) and CO2 fluxes that resolve key gaps in an emerging framework for using concurrent COS and CO2 measurements to quantify terrestrial gross primary productivity. At a wheat field in Oklahoma we found that in the peak growing season the flu...

  20. Carbonyl sulfide exchange in soils for better estimates of ecosystem carbon uptake

    OpenAIRE

    Whelan, Mary E.; Hilton, Timothy W; Berry, Joseph A; Berkelhammer, Max; Desai, Ankur R; Campbell, J. Elliott

    2016-01-01

    Carbonyl sulfide (COS) measurements are one of the emerging tools to better quantify gross primary production (GPP), the largest flux in the global carbon cycle. COS is a gas with a similar structure to CO2; COS uptake is thought to be a proxy for GPP. However, soils are a potential source or sink of COS. This study presents a framework for understanding soil–COS interactions. Excluding wetlands, most of the few observations of isolated soils that have been made show smal...

  1. Litter dominates surface fluxes of carbonyl sulfide in a Californian oak woodland

    OpenAIRE

    Sun, Wu; Maseyk, Kadmiel; Lett, Céline; Seibt, Ulli

    2016-01-01

    Carbonyl sulfide (COS) is a promising tracer for partitioning terrestrial photosynthesis and respiration from net carbon fluxes, based on its daytime co-uptake alongside CO2 through leaf stomata. Because ecosystem COS fluxes are the sum of plant and soil fluxes, using COS as a photosynthesis tracer requires accurate knowledge of soil COS fluxes. At an oak woodland in Southern California, we monitored below-canopy surface (soil + litter) COS and CO2 fluxes for 40 days using chambers and laser ...

  2. Exchange of carbonyl sulfide (COS) between the atmosphere and various soils in China

    OpenAIRE

    Liu, J; C. Geng; Mu, Y; Zhang, Y.; Xu, Z.; Wu, H

    2010-01-01

    Using a dynamic enclosure, the exchange rates of carbonyl sulfide (COS) between the atmosphere and 18 soils from 12 provinces in China were investigated. The emission or uptake of COS from the soils was highly dependent on the soil type, soil temperature, soil moisture, and atmospheric COS mixing ratio. In general, with the only exception being paddy soils, the soils in this investigation acted as sinks for atmospheric COS under wide ranges of soil temperature and soil moisture. Two intensive...

  3. Synthesis and Insecticidal Activity of Novel N-Pyridylpyrazole Carbonyl Thioureas

    Institute of Scientific and Technical Information of China (English)

    王宝雷; 马翼; 熊丽霞; 李正名

    2012-01-01

    A series of novel N-pyridylpyrazole carbonyl thioureas were designed and synthesized. Their structures were characterized by melting points, 1H NMR, IR and elemental analysis or HRMS. The bioassay tests indicated that some of these compounds exhibited moderate insecticidal activity against Mythirnna separata Walker and Culex pipiens pallens. Among 17 compounds, 5n and 5p showed 100% larvicidal activity against Mythimna separata Walker at the test concentration of 100 mg/L.

  4. Kinetic studies on vapor phase carbonylation of methanol to acetic acid over Rh/Ys catalyst

    Institute of Scientific and Technical Information of China (English)

    柳忠阳; 潘平来; 朱长城; 袁国卿

    1997-01-01

    A novel catalyst Rh/Ys for the carbonylation of methanol to acetic acid with CH3I as the promoter shows excellent activity and selectivity.The reaction is kinetically controlled.The reaction rate is in proportion to the concentration of Rh and CH3I but has nothing to do with those of CH3OHH and CO.The surface active energy is Ea ~51.02 kJ/mol.A mechanism is also proposed.

  5. Yttrium (III chloride catalyzed Mannich reaction: An efficient procedure for the synthesis of β-amino carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Venkateswarlu Yekkirala

    2014-12-01

    Full Text Available Yttrium (III chloride catalyzed Mannich reaction of aldehydes with ketones and amines in acetonitrile at reflux temperature to give various β-amino carbonyl compounds in very good yields.

  6. Antagonism between lipid-derived reactive carbonyls and phenolic compounds in the Strecker degradation of amino acids.

    Science.gov (United States)

    Delgado, Rosa M; Hidalgo, Francisco J; Zamora, Rosario

    2016-03-01

    The Strecker-type degradation of phenylalanine in the presence of 2-pentanal and phenolic compounds was studied to investigate possible interactions that either promote or inhibit the formation of Strecker aldehydes in food products. Phenylacetaldehyde formation was promoted by 2-pentenal and also by o- and p-diphenols, but not by m-diphenols. This is consequence of the ability of phenolic compounds to be converted into reactive carbonyls and produce the Strecker degradation of the amino acid. When 2-pentenal and phenolic compounds were simultaneously present, an antagonism among them was observed. This antagonism is suggested to be a consequence of the ability of phenolic compounds to either react with both 2-pentenal and phenylacetaldehyde, or compete with other carbonyl compounds for the amino acids, a function that is determined by their structure. All these results suggest that carbonyl-phenol reactions may be used to modulate flavor formation produced in food products by lipid-derived reactive carbonyls.

  7. Mitochondrial ascorbate-glutathione cycle and proteomic analysis of carbonylated proteins during tomato (Solanum lycopersicum) fruit ripening.

    Science.gov (United States)

    López-Vidal, O; Camejo, D; Rivera-Cabrera, F; Konigsberg, M; Villa-Hernández, J M; Mendoza-Espinoza, J A; Pérez-Flores, L J; Sevilla, F; Jiménez, A; Díaz de León-Sánchez, F

    2016-03-01

    In non-photosynthetic tissues, mitochondria are the main source of energy and of reactive oxygen species. Accumulation of high levels of these species in the cell causes damage to macromolecules including several proteins and induces changes in different metabolic processes. Fruit ripening has been characterized as an oxidative phenomenon; therefore, control of reactive oxygen species levels by mitochondrial antioxidants plays a crucial role on this process. In this work, ascorbate-glutathione cycle components, hydrogen peroxide levels and the proteomic profile of carbonylated proteins were analyzed in mitochondria isolated from tomato (Solanum lycopersicum) fruit at two ripening stages. A significant increase on most ascorbate-glutathione cycle components and on carbonylated proteins was observed in mitochondria from breaker to light red stage. Enzymes and proteins involved in diverse cellular and mitochondrial metabolic pathways were identified among the carbonylated proteins. These results suggest that protein carbonylation is a post-translational modification involved in tomato fruit ripening regulation.

  8. Synthesis and absorbing mechanism of two-layer microwave absorbers containing polycrystalline iron fibers and carbonyl iron

    Science.gov (United States)

    Ding, Qingwei; Zhang, Mingang; Zhang, Cunrui; Qian, Tianwei

    2013-04-01

    Polycrystalline iron fibers were fabricated by α-FeOOH fiber precursors. Two-layer microwave absorber had been prepared by as-prepared polycrystalline iron fibers and carbonyl iron. The structure, morphology and properties of the composites were characterized with X-ray diffraction, scanning electron microscope and Network Analyzer. The complex permittivity and reflection loss (dB) of the composites were measured employing vector network analyzer model PNA 3629D vector in the frequency range between 30 and 6000 MHz. The thickness effect of the carbonyl iron layer on the microwave loss properties of the composites was investigated. A possible microwave-absorbing mechanism of polycrystalline iron fibers/carbonyl iron composite was proposed. The polycrystalline iron fibers/carbonyl iron composite can find applications in suppression of electromagnetic interference, and reduction of radar signature.

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

    Science.gov (United States)

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

    2016-06-01

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

  10. Purification and characterization of a novel carbonyl reductase with high stereo-selectivity

    Institute of Scientific and Technical Information of China (English)

    YANG Ming; XU Yan; MU Xiaoqing; XIAO Rong

    2007-01-01

    A novel NADPH-dependent carbonyl reductase was separated from Candida parapsilosis CCTCC 203011.The enzyme gave a single band on sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE),which was purified through ammonium sulfate,Diethylamino Ethanol (DEAE) sepharose Fast flow (FF),phenyl-sepharose FF and blue sepharose FF chromatography from cell-free extract.The molecular mass of the enzyme was about 30 kDa.The optimum pH and temperature for reduction were 4.5℃ and 35℃,respectively.The Cu2+ had strong restrictive effect on enzyme activity.In addition,the carbonyl reductase was an enzyme with high substrate specificity and stereo-selectivity,and showed high asymmetric reduction activity towards α-hydroxyacetophenone and ethyl 4-chloro acetoacetate.For the asymmetric reduction of α-hydroxyacetophenone and ethyl 4-chloro acetoacetate,(S)-1-phenyl-1,2-ethanediol and (R)-ethyl 4-chloro-3-hydroxybutanoate were produced by the purified enzyme,with the 100% and 94.3% e.e.value,respectively.Therefore,the enzyme could be one of the effective biocatalysts for asymmetric synthesis of chiral alcohols.The amino acid sequences of one peptide from the purified enzyme were analyzed by LC-MASS-MASS,and the carbonyl reductase showed some identity to the hypothetical protein CaO 19.10414 reported.

  11. Effect of fiber material on ozone removal and carbonyl production from carpets

    Science.gov (United States)

    Abbass, Omed A.; Sailor, David J.; Gall, Elliott T.

    2017-01-01

    Indoor air quality is affected by indoor materials such as carpets that may act as sources and/or sinks of gas-phase air pollutants. Heterogeneous reactions of ozone with carpets may result in potentially harmful products. In this study, indoor residential carpets of varying fiber types were tested to evaluate their ability to remove ozone, and to assess their role in the production of carbonyls when exposed to elevated levels of ozone. Tests were conducted with six types of new unused carpets. Two sets of experiments were conducted, the first measured ozone removal and ozone deposition velocities, and the second measured primary carbonyl production and secondary production as a result of exposure to ozone. The tests were conducted using glass chambers with volume of 52 L each. Air exchange rates for all tests were 3 h-1. The ozone removal tests show that, for the conditions tested, the polyester carpet sample had the lowest ozone removal (40%), while wool carpet had the greatest ozone removal (65%). Most carpet samples showed higher secondary than primary carbonyl emissions, with carpets containing polypropylene fibers being a notable exception. Carpets with polyester fibers had both the highest primary and secondary emissions of formaldehyde among all samples tested. While it is difficult to make blanket conclusions about the relative air quality merits of various carpet fiber options, it is clear that ozone removal percentages and emissions of volatile organic compounds can vary drastically as a function of fiber type.

  12. Emissions of isoprene, monoterpene and short-chained carbonyl compounds from Eucalyptus spp. in southern Australia

    Science.gov (United States)

    Winters, Anthony J.; Adams, Mark A.; Bleby, Tim M.; Rennenberg, Heinz; Steigner, Dominik; Steinbrecher, Rainer; Kreuzwieser, Jürgen

    Eucalypts are among the highest emitters of biogenic volatile organic compounds, yet there is relatively little data available from field studies of this genus. Emissions of isoprene, monoterpenes and the short-chained carbonyls formaldehyde, acetaldehyde and acetone were determined from four species ( Eucalyptus camaldulensis, Eucalyptus globulus, Eucalyptus grandis, and Eucalytpus viminalis) in Australia. A smaller comparative study was conducted on E. camaldulensis in south-eastern Australia. Carbonyl emissions, reported here for the first time from eucalypts, were generally comparable with rates reported for other species, with diurnal emissions peaking at about 4, 75 and 34 nmol m -2 min -1 for acetone, formaldehyde and acetaldehyde respectively. There was wide variation in diurnal isoprene and monoterpene emissions between species, but under standard conditions, isoprene emissions were much lower than previous reports. Conversely, standard emission rates of monoterpenes were as much as six times greater than previous reports for some species. Emission of each carbonyl was correlated with its ambient concentration across different species, but more weakly related to temperature. Acetaldehyde emission in particular was significantly correlated with transpiration, but not with sap flow or with ethanol concentrations in xylem sap, suggesting fermentation within the leaf and stomatal conductance are primary controlling processes. Differences in acetaldehyde exchange velocities between sites, in addition to transpiration differences, suggest stomata may indeed exert long term emission regulation, in contrast to compounds for which no biological sink exists.

  13. Nitrite promotes protein carbonylation and Strecker aldehyde formation in experimental fermented sausages: are both events connected?

    Science.gov (United States)

    Villaverde, A; Ventanas, J; Estévez, M

    2014-12-01

    The role played by curing agents (nitrite, ascorbate) on protein oxidation and Strecker aldehyde formation is studied. To fulfill this objective, increasing concentrations of nitrite (0, 75 and 150ppm) and ascorbate (0, 250 and 500ppm) were added to sausages subjected to a 54day drying process. The concurrence of intense proteolysis, protein carbonylation and formation of Strecker aldehydes during processing of sausages suggests that α-aminoadipic semialdehyde (AAS) and γ-glutamic semialdehyde (GGS) may be implicated in the formation of Strecker aldehydes. The fact that nitrite (150ppm, ingoing amount) significantly promoted the formation of protein carbonyls at early stages of processing and the subsequent formation of Strecker aldehydes provides strength to this hypothesis. Ascorbate (125 and 250ppm) controlled the overall extent of protein carbonylation in sausages without declining the formation of Strecker aldehydes. These results may contribute to understanding the chemistry fundamentals of the positive influence of nitrite on the flavor and overall acceptability of cured muscle foods.

  14. Cranberry phytochemicals inhibit glycation of human hemoglobin and serum albumin by scavenging reactive carbonyls.

    Science.gov (United States)

    Liu, Haiyan; Liu, Hanwei; Wang, Wei; Khoo, Christina; Taylor, James; Gu, Liwei

    2011-08-01

    Protein glycation caused by sugars and reactive carbonyls is a contributing factor to diabetic complications, aging, and other chronic diseases. The objective of this study was to investigate the inhibitory effects of cranberry phytochemicals on protein glycation. Cranberries, purified to yield sugar-free phytochemical powder, were fractionated into ethyl acetate and water fractions. Water fraction was further separated into water fraction I, II, and III on a Sephadex LH-20 column. Cranberry phytochemical powder and its fractions significantly inhibited the formation of glycated hemoglobin. The concentrations of cranberry phytochemicals required to inhibit 50% of albumin glycation (EC(50)) in albumin-glucose assay were lower than that of aminoguanidine except for water fraction I. Cranberry phytochemicals inhibited glycation of human serum albumin mediated by methylglyoxal, but the EC(50) were higher than that of aminoguanidine. Carbonyl scavenging assay showed that water fraction II scavenged 89.3% of methylglyoxal at 6 h of reaction. Fractions enriched with procyanidins showed higher antiglycation activities, suggesting procyanidins were the major active components. The hypothesis whether cranberry procyanidins scavenged reactive carbonyls by forming adducts was tested. Epicatechin was used as a model compound to react with methylglyoxal and glyoxal at pH 7.4. Five adducts were detected and their structures were tentatively identified using HPLC-ESI-MS/MS.

  15. Seasonal behavior of carbonyls and source characterization of formaldehyde (HCHO) in ambient air

    Science.gov (United States)

    Lui, K. H.; Ho, Steven Sai Hang; Louie, Peter K. K.; Chan, C. S.; Lee, S. C.; Hu, Di; Chan, P. W.; Lee, Jeffrey Chi Wai; Ho, K. F.

    2017-03-01

    Gas-phase formaldehyde (HCHO) is an intermediate and a sensitive indicator for volatile organic compounds (VOCs) oxidation, which drives tropospheric ozone production. Effective photochemical pollution control strategies demand a thorough understanding of photochemical oxidation precursors, making differentiation between sources of primary and secondary generated HCHO inevitable. Spatial and seasonal variations of airborne carbonyls based on two years of measurements (2012-2013), coupled with a correlation-based HCHO source apportionment analysis, were determined for three sampling locations in Hong Kong (denoted HT, TC, and YL). Formaldehyde and acetaldehyde were the two most abundant compounds of the total quantified carbonyls. Pearson's correlation analysis (r > 0.7) implies that formaldehyde and acetaldehyde possibly share similar sources. The total carbonyl concentration trends (HT urban > rural). A regression analysis further quantifies the relative primary HCHO source contributions at HT (∼13%), TC (∼21%), and YL (∼40%), showing more direct vehicular emissions in urban than rural areas. Relative secondary source contributions at YL (∼36%) and TC (∼31%) resemble each other, implying similar urban source contributions. Relative background source contributions at TC could be due to a closed structure microenvironment that favors the trapping of HCHO. Comparable seasonal differences are observed at all stations. The results of this study will aid in the development of a new regional ozone (O3) control policy, as ambient HCHO can enhance O3 production and also be produced from atmospheric VOCs oxidation (secondary HCHO).

  16. Synthesis of 3-[(N-Carboalkoxy)ethylamino]-indazole-dione Derivatives and Their Biological Activities on Human Liver Carbonyl Reductase

    OpenAIRE

    Berhe, Solomon; Slupe, Andrew; Luster, Choice; Charlier, Henry A.; Warner, Don L.; Zalkow, Leon H.; Burgess, Edward M.; Enwerem, Nkechi M.; Bakare, Oladapo

    2009-01-01

    A series of indazole-dione derivatives were synthesized by the 1,3-dipolar cycloaddition reaction of appropriate substituted benzoquinones or naphthoquinones and N-carboalkoxyamino diazopropane derivatives. These compounds were evaluated for their effects on human carbonyl reductase. Several of the analogs were found to serve as substrates for carbonyl reductase with a wide range of catalytic efficiencies, while four analogs display inhibitory activities with IC50 values ranging from 3 – 5 μM...

  17. Spatial distributions of and diurnal variations in low molecular weight carbonyl compounds in coastal seawater, and the controlling factors

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Kazuhiko, E-mail: takedaq@hiroshima-u.ac.jp [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan); Katoh, Shinya; Mitsui, Yumi; Nakano, Shinichi [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan); Nakatani, Nobutake [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan); Department of Environmental and Symbiotic Sciences, Rakuno Gakuen University, 582 Bunkyodai-Midorimachi, Ebetsu, Hokkaido 069-8501 (Japan); Sakugawa, Hiroshi [Graduate School of Biosphere Science, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan)

    2014-09-15

    We studied the spatial distributions of and the diurnal variations in four low molecular weight (LMW) carbonyl compounds, formaldehyde, acetaldehyde, propionaldehyde, and glyoxal, in coastal seawater. The samples were taken from the coastal areas of Hiroshima Bay, the Iyo Nada, and the Bungo Channel, western Japan. The formaldehyde, acetaldehyde, and glyoxal concentrations were higher in the northern part of Hiroshima Bay than at offshore sampling points in the Iyo Nada and the Bungo Channel. These three compounds were found at much higher concentrations in the surface water than in deeper water layers in Hiroshima Bay. It is noteworthy that propionaldehyde was not detected in any of the seawater samples, the concentrations present being lower than the detection limit (1 nanomole per liter (nM)) of the high performance liquid chromatography (HPLC) system we used. Photochemical and biological experiments were performed in the laboratory to help understand the characteristic distributions and fates of the LMW carbonyl compounds. The primary process controlling their fate in the coastal environment appears to be their biological consumption. The direct photo degradation of propionaldehyde, initiated by ultraviolet (UV) absorption, was observed, although formaldehyde and acetaldehyde were not degraded by UV irradiation. Our results suggest that the degradation of the LMW carbonyl compounds by photochemically formed hydroxyl radicals is relatively insignificant in the study area. Atmospheric deposition is a possible source of soluble carbonyl compounds in coastal surface seawater, but it may not influence the carbonyl concentrations in offshore waters. - Highlights: • Low molecular weight (LMW) carbonyl compounds in coastal seawater were determined. • Photochemical productions of LMW carbonyl compounds in seawater were observed. • LMW carbonyl compounds were largely consumed biologically. • Photochemical degradation was relatively insignificant in the study area.

  18. Soil atmosphere exchange of Carbonyl Sulfide (COS) regulated by diffusivity depending on water-filled pore space

    OpenAIRE

    H. Van Diest; Kesselmeier, J.

    2007-01-01

    The exchange of carbonyl sulfide (COS) between soil and the atmosphere was investigated for three arable soils from Germany, China and Finland and one forest soil from Siberia for parameterization in the relation to ambient carbonyl sulfide (COS) concentration, soil water content (WC) and air temperature. All investigated soils acted as significant sinks for COS. A clear and distinct uptake optimum was found for the German, Chinese, Finnish and Siberian soils at 11.5%, 9%, 11.5%, and 9% soil ...

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

    Science.gov (United States)

    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.

  20. Fumigation with carbonyl sulfide: a model for the interaction of concentration, time and temperature.

    Science.gov (United States)

    Weller, G L.; Morton, R

    2001-10-01

    The new fumigant carbonyl sulfide offers an alternative to both methyl bromide and phosphine as a grain fumigant. Separate mathematical models for levels of kill, based on quantitative toxicological studies were developed for adults and eggs of the rice weevil Sitophilus oryzae (L.). These models suggest that fumigation exposure times for carbonyl sulfide will be a compromise between those of methyl bromide (typically 24h) and phosphine (7-10d) to achieve a very high kill of all developmental stages. S. oryzae eggs were more difficult to kill with carbonyl sulfide fumigation than the adults. At 30 degrees C, a 25gm(-3) fumigation killed 99.9% of adults in less than 1d, but took 4d to kill the same percentage of eggs. Models were generated to describe the mortality of adults at 10, 15, 20, 25 and 30 degrees C. From these models it is predicted that fumigation with carbonyl sulfide for 1-2d at 30gm(-3) will kill 99.9% of adults. Furthermore the models illustrate that fumigations with concentrations below 10gm(-3) are unlikely to kill all adult S. oryzae. Significant variation was observed in the response of eggs to the fumigant over the temperature range of 10 to 30 degrees C. Models were generated to describe the mortality of eggs at 10, 15, 20, 25 and 30 degrees C. As the temperature was reduced below 25 degrees C, the time taken to achieve an effective fumigation increased. Extrapolating from the models, a 25gm(-3) fumigation to control 99.9% of S. oryzae eggs will take 95h (4d) at 30 degrees C, 77h (3.2d) at 25 degrees C, 120h (5d) at 20 degrees C, 174h (7.5d) at 15 degrees C and about 290h (11d) at 10 degrees C. The role of temperature in the time taken to kill eggs with carbonyl sulfide cannot be ignored. In order to achieve the desired level of kill of all developmental stages, the fumigation rates need to be set according to the most difficult life stage to kill, in this instance, the egg stage.

  1. Cross-talk between lipid and protein carbonylation in a dynamic cardiomyocyte model of mild nitroxidative stress

    Directory of Open Access Journals (Sweden)

    Eva Griesser

    2017-04-01

    Full Text Available Reactive oxygen and nitrogen species (ROS/RNS play an important role in the regulation of cardiac function. Increase in ROS/RNS concentration results in lipid and protein oxidation and is often associated with onset and/or progression of many cardiovascular disorders. However, interplay between lipid and protein modifications has not been simultaneously studied in detail so far. Biomolecule carbonylation is one of the most common biomarkers of oxidative stress. Using a dynamic model of nitroxidative stress we demonstrated rapid changes in biomolecule carbonylation in rat cardiomyocytes. Levels of carbonylated species increased as early as 15 min upon treatment with the peroxynitrite donor, 3-morpholinosydnonimine (SIN-1, and decreased to values close to control after 16 h. Total (lipids+proteins vs. protein-specific carbonylation showed different dynamics, with a significant increase in protein-bound carbonyls at later time points. Treatment with SIN-1 in combination with inhibitors of proteasomal and autophagy/lysosomal degradation pathways allowed confirmation of a significant role of the proteasome in the degradation of carbonylated proteins, whereas lipid carbonylation increased in the presence of autophagy/lysosomal inhibitors. Electrophilic aldehydes and ketones formed by lipid peroxidation were identified and relatively quantified using LC-MS/MS. Molecular identity of reactive species was used for data-driven analysis of their protein targets. Combination of different enrichment strategies with LC-MS/MS analysis allowed identification of more than 167 unique proteins with 332 sites modified by electrophilic lipid peroxidation products. Gene ontology analysis of modified proteins demonstrated enrichment of several functional categories including proteins involved in cytoskeleton, extracellular matrix, ion channels and their regulation. Using calcium mobilization assays, the effect of nitroxidative stress on the activity of several ion

  2. Protein conjugated with aldehydes derived from lipid peroxidation as an independent parameter of the carbonyl stress in the kidney damage

    Directory of Open Access Journals (Sweden)

    Medina-Navarro Rafael

    2011-11-01

    Full Text Available Abstract Background One of the well-defined and characterized protein modifications usually produced by oxidation is carbonylation, an irreversible non-enzymatic modification of proteins. However, carbonyl groups can be introduced into proteins by non-oxidative mechanisms. Reactive carbonyl compounds have been observed to have increased in patients with renal failure. In the present work we have described a procedure designed as aldehyde capture to calculate the protein carbonyl stress derived solely from lipid peroxidation. Methods Acrolein-albumin adduct was prepared as standard at alkaline pH. Rat liver microsomal membranes and serum samples from patients with diabetic nephropathy were subjected to the aldehyde capture procedure and aldol-protein formation. Before alkalinization and incubation, samples were precipitated and redisolved in 6M guanidine. The absorbances of the samples were read with a spectrophotometer at 266 nm against a blank of guanidine. Results Evidence showed abundance of unsaturated aldehydes derived from lipid peroxidation in rat liver microsomal membranes and in the serum of diabetic patients with advanced chronic kidney disease. Carbonyl protein and aldol-proteins resulted higher in the diabetic nephropathy patients (p Conclusion The aldehyde-protein adduct represents a non oxidative component of carbonyl stress, independent of the direct amino acid oxidation and could constitute a practical and novelty strategy to measure the carbonyl stress derived solely from lipid peroxidation and particularly in diabetic nephropathy patients. In addition, we are in a position to propose an alternative explanation of why alkalinization of urine attenuates rhabdomyolysis-induced renal dysfunction.

  3. Assignment of congested NMR spectra: Carbonyl backbone enrichment via the Entner Doudoroff pathway

    Science.gov (United States)

    Goldbourt, Amir; Day, Loren A.; McDermott, Ann E.

    2007-12-01

    In NMR spectra of complex proteins, sparse isotope enrichment can be important, in that the removal of many 13C- 13C homonuclear J-couplings can narrow the lines and thereby facilitate the process of spectral assignment and structure elucidation. We present a simple scheme for selective yet extensive isotopic enrichment applicable for production of proteins in organisms utilizing the Entner-Doudoroff (ED) metabolic pathway. An enrichment scheme so derived is demonstrated in the context of a magic-angle spinning solid-state NMR (MAS SSNMR) study of Pf1 bacteriophage, the host of which is Pseudomonas aeruginosa, strain K (PAK), an organism that uses the ED pathway for glucose catabolism. The intact and infectious Pf1 phage in this study was produced by infected PAK cells grown on a minimal medium containing 1- 13C D-glucose ( 13C in position 1) as the sole carbon source, as well as 15NH 4Cl as the only nitrogen source. The 37 MDa Pf1 phage consists of about 93% major coat protein, 1% minor coat proteins, and 6% single-stranded, circular DNA. As a consequence of this composition and the enrichment scheme, the resonances in the MAS SSNMR spectra of the Pf1 sample were almost exclusively due to carbonyl carbons in the major coat protein. Moreover, 3D heteronuclear NCOCX correlation experiments also show that the amino acids leucine, serine, glycine, and tyrosine were not isotopically enriched in their carbonyl positions (although most other amino acids were), which is as expected based upon considerations of the ED metabolic pathway. 3D NCOCX NMR data and 2D 15N- 15N data provided strong verification of many previous assignments of 15N amide and 13C carbonyl shifts in this highly congested spectrum; both the semi-selective enrichment patterns and the narrowed linewidths allowed for greater certainty in the assignments as compared with use of uniformly enriched samples alone.

  4. Sol–gel method as a way of carbonyl iron powder surface modification for interaction improvement

    Energy Technology Data Exchange (ETDEWEB)

    Małecki, P., E-mail: pawel.malecki@pwr.edu.pl [Polymer Engineering and Technology Division, W-3, Wrocław University of Technology, Smoluchowskiego 25, 50 370 Wrocław (Poland); Kolman, K.; Pigłowski, J. [Polymer Engineering and Technology Division, W-3, Wrocław University of Technology, Smoluchowskiego 25, 50 370 Wrocław (Poland); Kaleta, J. [Department of Mechanics, Materials Science and Engineering, W-10, Wrocław University of Technology, Smoluchowskiego 25, 50-370 Wrocław (Poland); Krzak, J., E-mail: justyna.krzak@pwr.edu.pl [Department of Mechanics, Materials Science and Engineering, W-10, Wrocław University of Technology, Smoluchowskiego 25, 50-370 Wrocław (Poland)

    2015-03-15

    This article presents a method for modification of carbonyl iron particles’ surface (CIP), (d{sub 50}=4–9 µm) by silica coatings obtained using the sol–gel method. Reaction parameters were determined to obtain dry magnetic powder with homogeneous silica coatings without further processing and without any by-product in the solid or liquid phase. This approach is new among the commonly used methods of silica coating of iron particles. No attempt has been made to cover a carbonyl iron surface by silica in a waste-free method, up to date. In the current work two different silica core/shell structures were made by the sol–gel process, based on different silica precursors: tetraethoxy-silane (TEOS) and tetramethoxy-silane (TMOS). The dependence between the synthesis procedure and thickness of silica shell covering carbonyl iron particles has been described. Surface morphology of the modified magnetic particles and the coating thickness were characterized with the use of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Determination of the physicochemical structure of the obtained materials was performed by the energy-dispersive X-ray spectroscope (EDS), and the infrared technique (IR). The surface composition was analyzed using X-ray photoelectron spectroscopy (XPS). Additionally, distribution of particle size was measured using light microscopy. The new, efficient process of covering micro-size CIP with a nanometric silica layer was shown. Results of a performed analysis confirm the effectiveness of the presented method. - Highlights: • Proper covering CIP by sol–gel silica layer avoids agglomeration. • A new solid waste-free method of CIP coating is proposed. • Examination of the properties of modified CIP in depends on washing process. • Coatings on CIP particles doesn’t change the magnetic properties of particles.

  5. STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A BIDENTATE POLYMER BOUND CIS-DICARBONYLRHODIUM COMPLEX AS CATALYST

    Institute of Scientific and Technical Information of China (English)

    WANG Xiaojun; LIU Zhongyang; PAN Pinglai; YUAN Guoqing

    1996-01-01

    Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodium used as a catalyst for carbonylation of methanol to acetic acid and anhydride has been studied. The structural characteristics of the copolymer ligand and complex, and the influences of the reaction conditions on the carbonylation catalyzed by this polymer complex have been investigated. In comparison with small molecule catalyst of Rh complex, the bidentate copolymer coordinated complex has better thermal stability. The reaction mechanism of the carbonylation reaction is also illustrated.

  6. A green synthesis of α,β-unsaturated carbonyl compounds from glyceraldehyde acetonide

    Directory of Open Access Journals (Sweden)

    Cláudia O. Veloso

    2011-01-01

    Full Text Available The catalytic behavior of Cs-exchanged and Cs-impregnated zeolites (X and Y was studied using the Knoevenagel condensation between glyceraldehyde acetonide and ethyl acetoacetate in order to produce the corresponding α,β-unsaturated carbonyl compound that is an important intermediate for fine chemicals. The influence of reaction temperature, type of zeolite, and basicity of the sites on the catalytic behavior of the samples was evaluated. All zeolites were active for the studied reaction. The formation of the main condensation product was favored at lower reaction temperatures. Products of further condensations were also observed especially for samples that were only dried before catalytic test.

  7. Electromagnetic properties of carbonyl iron and their microwave absorbing characterization as filler in silicone rubber

    Indian Academy of Sciences (India)

    Yuping Duan; Guofang Li; Lidong Liu; Shunhua Liu

    2010-10-01

    The complex permittivity, permeability and microwave-absorbing properties of rubber composites filled with carbonyl iron are measured at frequencies from 2–18 GHz. The results indicate that the reflection loss peak shifts towards low frequency region with increasing layer thickness or increasing weight concentration. The minimum reflection loss value of –23.06 dB was obtained at 3.3 GHz for the composites with 80% wt. These results show that the composites possess good microwave absorbing ability in both low- and highfrequency bands.

  8. Pd-catalyzed carbonylative α-arylation of aryl bromides: scope and mechanistic studies.

    Science.gov (United States)

    Nielsen, Dennis U; Lescot, Camille; Gøgsig, Thomas M; Lindhardt, Anders T; Skrydstrup, Troels

    2013-12-23

    Reaction conditions for the three-component synthesis of aryl 1,3-diketones are reported applying the palladium-catalyzed carbonylative α-arylation of ketones with aryl bromides. The optimal conditions were found by using a catalytic system derived from [Pd(dba)2] (dba=dibenzylideneacetone) as the palladium source and 1,3-bis(diphenylphosphino)propane (DPPP) as the bidentate ligand. These transformations were run in the two-chamber reactor, COware, applying only 1.5 equivalents of carbon monoxide generated from the CO-releasing compound, 9-methylfluorene-9-carbonyl chloride (COgen). The methodology proved adaptable to a wide variety of aryl and heteroaryl bromides leading to a diverse range of aryl 1,3-diketones. A mechanistic investigation of this transformation relying on 31P and 13C NMR spectroscopy was undertaken to determine the possible catalytic pathway. Our results revealed that the combination of [Pd(dba)2] and DPPP was only reactive towards 4-bromoanisole in the presence of the sodium enolate of propiophenone suggesting that a [Pd(dppp)(enolate)] anion was initially generated before the oxidative-addition step. Subsequent CO insertion into an [Pd(Ar)(dppp)(enolate)] species provided the 1,3-diketone. These results indicate that a catalytic cycle, different from the classical carbonylation mechanism proposed by Heck, is operating. To investigate the effect of the dba ligand, the Pd0 precursor, [Pd(η3-1-PhC3H4)(η5-C5H5)], was examined. In the presence of DPPP, and in contrast to [Pd(dba)2], its oxidative addition with 4-bromoanisole occurred smoothly providing the [PdBr(Ar)(dppp)] complex. After treatment with CO, the acyl complex [Pd(CO)Br(Ar)(dppp)] was generated, however, its treatment with the sodium enolate led exclusively to the acylated enol in high yield. Nevertheless, the carbonylative α-arylation of 4-bromoanisole with either catalytic or stoichiometric [Pd(η3-1-PhC3H4)(η5-C5H5)] over a short reaction time, led to the 1,3-diketone product

  9. Non-enzymatic modification of aminophospholipids by carbonyl-amine reactions.

    Science.gov (United States)

    Naudí, Alba; Jové, Mariona; Ayala, Victòria; Cabré, Rosanna; Portero-Otín, Manuel; Pamplona, Reinald

    2013-02-05

    Non-enzymatic modification of aminophospholipids by lipid peroxidation-derived aldehydes and reducing sugars through carbonyl-amine reactions are thought to contribute to the age-related deterioration of cellular membranes and to the pathogenesis of diabetic complications. Much evidence demonstrates the modification of aminophospholipids by glycation, glycoxidation and lipoxidation reactions. Therefore, a number of early and advanced Maillard reaction-lipid products have been detected and quantified in different biological membranes. These modifications may be accumulated during aging and diabetes, introducing changes in cell membrane physico-chemical and biological properties.

  10. A Device-Independent Evaluation of Carbonyl Emissions from Heated Electronic Cigarette Solvents

    Science.gov (United States)

    Chen, Wenhao; Liao, Jiawen; Matsuo, Toshiki; Ito, Kazuhide; Fowles, Jeff; Shusterman, Dennis; Mendell, Mark; Kumagai, Kazukiyo

    2017-01-01

    Objectives To investigate how the two main electronic (e-) cigarette solvents—propylene glycol (PG) and glycerol (GL)—modulate the formation of toxic volatile carbonyl compounds under precisely controlled temperatures in the absence of nicotine and flavor additives. Methods PG, GL, PG:GL = 1:1 (wt/wt) mixture, and two commercial e-cigarette liquids were vaporized in a stainless steel, tubular reactor in flowing air ranging up to 318°C to simulate e-cigarette vaping. Aerosols were collected and analyzed to quantify the amount of volatile carbonyls produced with each of the five e-liquids. Results Significant amounts of formaldehyde and acetaldehyde were detected at reactor temperatures ≥215°C for both PG and GL. Acrolein was observed only in e-liquids containing GL when reactor temperatures exceeded 270°C. At 318°C, 2.03±0.80 μg of formaldehyde, 2.35±0.87 μg of acetaldehyde, and a trace amount of acetone were generated per milligram of PG; at the same temperature, 21.1±3.80 μg of formaldehyde, 2.40±0.99 μg of acetaldehyde, and 0.80±0.50 μg of acrolein were detected per milligram of GL. Conclusions We developed a device-independent test method to investigate carbonyl emissions from different e-cigarette liquids under precisely controlled temperatures. PG and GL were identified to be the main sources of toxic carbonyl compounds from e-cigarette use. GL produced much more formaldehyde than PG. Besides formaldehyde and acetaldehyde, measurable amounts of acrolein were also detected at ≥270°C but only when GL was present in the e-liquid. At 215°C, the estimated daily exposure to formaldehyde from e-cigarettes, exceeded United States Environmental Protection Agency (USEPA) and California Office of Environmental Health Hazard Assessment (OEHHA) acceptable limits, which emphasized the need to further examine the potential cancer and non-cancer health risks associated with e-cigarette use. PMID:28076380

  11. Determination of carbonyl compounds in air by HPLC; Determinacion de compuestos carbonilicos en aire por HPLC

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, S.; Perez, R.M.; Campos, A.; Gonzalez, D.

    1995-07-01

    A method for the determination of seven carbonyl compounds in air is presented. The procedure involve sampling of air by a Sep-Pak Cartridge impregnated with 2,4-dinitrophenylhydrazine. Elution was done with 3 mL of acetonitrile and the eluate was diluted to 5 mL. The analysis was done by HPLC with UV detection and external standard method quantification. It has been achieved relative standard deviations about 5% and detection limits of 80 ng/cartridge for formaldehyde, acetaldehyde and acetoacetonitrile. Three different types of samples (rural, urban, petrol emission) were successfully analyzed. (Author) 12 refs.

  12. Calculation of High Frequency Complex Permeability of Carbonyl Iron Flakes in a Nomagnetic Matrix

    Institute of Scientific and Technical Information of China (English)

    WEN Fu-Sheng; QIAO Liang; YI Hai-Bo; ZHOU Dong; LI Fa-Shen

    2008-01-01

    The carbonyl iron flakes are fabricated by high-energy ball milling.The effective permeability is measured and calculated for the composite consisting of flakes embedded in a nonmagnetic matrix.The magnetic flakes with a shape anisotropy and random spatial distribution of normal direction are considered to calculate the complex permeability of magnetic flake materials.Its analytical model is derived from the Landau-Lifshitz- Gilbert equation and Bruggeman's effective medium theory.The calculated results agree well with the experiment.

  13. LASER-INDUCED DECOMPOSITION OF METAL CARBONYLS FOR CHEMICAL VAPOR DEPOSITION OF MICROSTRUCTURES

    OpenAIRE

    1989-01-01

    Tungsten and nickel carbonyls were used to produce metal microstructures by laser-induced chemical vapor deposition (CVD) on various substrates. The deposition rate of microstructures produced by thermodecomposition of W(CO)6 on Si substrates heated with a cw Ar+ laser beam was relatively low (10 to 30 nm/s) even at high temperatures (above 900°C). Ni microstructures were deposited on quartz substrates irradiated with a CO2 laser beam. Relatively high laser powers were needed to heat the Ni s...

  14. Organocatalyzed Asymmetric α-Oxidation, α-Aminoxylation and α-Amination of Carbonyl Compounds

    Directory of Open Access Journals (Sweden)

    Worawan Bhanthumnavin

    2010-02-01

    Full Text Available Organocatalytic asymmetric α-oxidation and amination reactions of carbonyl compounds are highly useful synthetic methodologies, especially in generating chiral building blocks that previously have not been easily accessible by traditional methods. The concept is relatively new and therefore the list of new catalysts, oxidizing and aminating reagents, as well as new substrates, are expanding at an amazing rate. The scope of this review includes new reactions and catalysts, mechanistic aspects and synthetic applications of α-oxidation, hydroxylation, aminoxylation, amination, hydrazination, hydroxyamination and related α-heteroatom functionalization of aldehydes, ketones and related active methylene compounds published during 2005–2009.

  15. Contribution of carbonyl photochemistry to aging of atmospheric secondary organic aerosol

    DEFF Research Database (Denmark)

    Mang, Stephen A.; Henricksen, Dana K.; Bateman, Adam P.

    2008-01-01

    in situ by infrared cavity ring-down spectroscopy. A number of additional gas-phase products of SOA photodegradation were observed by gas chromatography, including methane, ethene, acetaldehyde, acetone, methanol, and I-butene. The absorption spectrum of SOA material collected onto CaF, windows...... of freshly prepared SOA was estimated to be on the order of' 15 L mol(-1) cm(-1) at 300 rim, implying one carbonyl group in every SOA constituent. The absorption by the SOA material slowly increased in the visible and near-UV during storage of SOA in open air in the dark, presumably as a result...

  16. Sensitivity of Saccharomyces cerevisiae defective in TOR signaling pathway to carbonyl/oxidative stress

    Directory of Open Access Journals (Sweden)

    Valishkevych B. V.

    2014-09-01

    Full Text Available Aim. To investigate the influence of carbonyl/oxidative stress induced by glyoxal, methylglyoxal and hydrogen peroxide on the survival of Saccharomyces cerevisiae, defective for different parts of TOR- signaling pathway, grown on glucose or fructose. Methods. The assessment of number of colony-forming units to determine the yeast reproductive ability. Results. It was shown that at certain concentrations the mentioned above toxicants caused an increase in yeast survival, indicating the hormetic effect. Conclusions. The TOR signaling pathway is involved in the hormetic effect, but it is specific for each strain and depends on the type of carbohydrate in the incubation medium.

  17. Catalytic Enantioselective Electrophilic Aminations of Acyclic α-Alkyl β-Carbonyl Nucleophilies.

    Science.gov (United States)

    Liu, Xiaofeng; Sun, Bingfeng; Deng, Li

    2009-06-01

    Highly enantioselective aminations of acyclic α-alkyl β-keto thioesters and trifluoroethyl α-methyl α-cyanoacetate (12) with as low as 0.05 mol % of a bifunctional cinchona alkaloid catalyst were established. This ability to afford highly enantioselectivity for the amination of α-alkyl β-carbonyl compounds renders the 6'-OH cinchona alkaloid-catalyzed amination applicable for the enantioselective synthesis of acyclic chiral compounds bearing N-substituted quaternary stereocenters. The synthetic application of this reaction is illustrated in a concise asymmetric synthesis of α-methylserine, a key intermediate previously utilized in the total synthesis of a small molecule immunomodulator, conagenin.

  18. (Uncertain) Carbonyl Sulfide Plant Fluxes Spatially Constrain (Even More Uncertain) CO2 GPP

    Science.gov (United States)

    Hilton, T. W.; Whelan, M.; Kulkarni, S.; Zumkehr, A. L.; Berry, J. A.; Campbell, J. E.

    2015-12-01

    With predictions of future terrestrial carbon dioxide (CO2)gross primary productivity (GPP) remaining stubbornly uncertain,ecosystem carbonyl sulfide (COS) fluxes provide an independent source ofinformation that may be able to reduce that uncertainty. Several openquestions must be addressed before COS may be applied widely as a GPPtracer. Here we employ an atmospheric chemistry and transport model(STEM) and airborne atmospheric COS concentration observations todemonstrate that COS plant uptake spatially constrains CO2 GPP even whenaccounting for soil COS flux uncertainty and COS leaf-scale relativeuptake variability and uncertainty.

  19. Hepatocyte cytotoxicity induced by hydroperoxide (oxidative stress model) or glyoxal (carbonylation model): prevention by bioactive nut extracts or catechins.

    Science.gov (United States)

    Banach, Monica S; Dong, Qiang; O'Brien, Peter J

    2009-03-16

    Carbonyl and oxidative stress play important roles in the development of diabetic complications and have been shown to be augmented by various natural compounds and pharmacological agents. Nuts are a rich source of bioactive compounds and antioxidants and various beneficial health effects of nuts have been reported. This study was conducted to evaluate the cytoprotectiveness of various nut extracts and bioactive compounds found in nuts for decreasing cytotoxicity, lipid peroxidation and protein carbonylation in cell toxicity models of diabetes-related carbonyl (glyoxal) and oxidative stress (hydroperoxide). Methanol, ethyl acetate or water were used to prepare crude hazelnut and walnut extracts, which were then used to screen for in vitro cytoprotection of freshly isolated rat hepatocytes against these toxins. The order of protection by nut extracts against hydroperoxide induced cell death was: walnut methanolic extract>walnut aqueous extract>lipophilic walnut extract>hazelnut aqueous extract>hazelnut methanolic extract whereas the lipophilic hazelnut extract did not protect against cell death. The order of protection against lipid peroxidation was the same except for the hazelnut methanolic extract, which prevented lipid peroxidation better than the hazelnut aqueous extract. Catechin, epicatechin and epigallocatechin gallate (EGCG) were investigated for possible protective effects against carbonyl stress cell death and protein carbonylation in hepatocytes. Catechin protected against glyoxal induced cell death and protein carbonylation, and even elicited protection when added to hepatocytes 30 min after the addition of glyoxal. When catechin and epicatechin were compared for protectiveness against glyoxal induced carbonyl stress in hepatocytes, epicatechin protected more effectively than catechin against cell death and protein carbonylation at 120 min. Both compounds also elicited better protection when premixed with glyoxal before addition to hepatocytes, compared

  20. Aldehyde dehydrogenase 2 activation in aged heart improves the autophagy by reducing the carbonyl modification on SIRT1.

    Science.gov (United States)

    Wu, Bing; Yu, Lu; Wang, Yishi; Wang, Hongtao; Li, Chen; Yin, Yue; Yang, Jingrun; Wang, Zhifa; Zheng, Qiangsun; Ma, Heng

    2016-01-19

    Cardiac aging is characterized by accumulation of damaged proteins and decline of autophagic efficiency. Here, by forestalling SIRT1 carbonylated inactivation in aged heart, we determined the benefits of activation of aldehyde dehydrogenase 2 (ALDH2) on the autophagy. In this study, the ALDH2 KO mice progressively developed age-related heart dysfunction and showed reduction in the life span, which strongly suggests that ALDH2 ablation leads to cardiac aging. What's more, aged hearts displayed a significant decrease ALDH2 activity, resulting in accumulation of 4-HNE-protein adducts and protein carbonyls, impairment in the autophagy flux, and, consequently, deteriorated cardiac function after starvation. Sustained Alda-1 (selective ALDH2 activator) treatment increased cardiac ALDH2 activity and abrogated these effects. Using SIRT1 deficient heterozygous (Sirt1+/-) mice, we found that SIRT1 was necessary for ALDH2 activation-induced autophagy. We further demonstrated that ALDH2 activation attenuated SIRT1 carbonylation and improved SIRT1 activity, thereby increasing the deacetylation of nuclear LC3 and FoxO1. Sequentially, ALDH2 enhanced SIRT1 regulates LC3-Atg7 interaction and FoxO1 increased Rab7 expression, which were both necessary and sufficient for restoring autophagy flux. These results highlight that both accumulation of proteotoxic carbonyl stress linkage with autophagy decline contribute to heart senescence. ALDH2 activation is adequate to improve the autophagy flux by reducing the carbonyl modification on SIRT1, which in turn plays an important role in maintaining cardiac health during aging.

  1. Amelioration of age-dependent increase in protein carbonyls of cerebral hemispheres of mice by melatonin and ascorbic acid.

    Science.gov (United States)

    Dkhar, Preeticia; Sharma, Ramesh

    2011-12-01

    Melatonin secreted by the pineal gland acts as a free radical scavenger besides its role as a hormonal signaling agent. It detoxifies a variety of free radicals and reactive oxygen intermediates including hydroxyl radical, peroxynitrite anion and singlet oxygen. Ascorbic acid (Vitamin C), a water soluble vitamin, is a naturally occurring antioxidant and cofactor in various enzymes. Protein carbonyls are formed as a consequence of the oxidative modification of proteins by reactive oxygen species. Oxidative modification alters the function of protein and is thought to play an important role in the decline of cellular functions during aging. In the present study, the effect of melatonin and ascorbic acid on age-related carbonyl content of cerebral hemispheres in mice was investigated. Protein carbonyls of cerebral hemispheres have been found to be significantly higher in 18-month-old mice as compared to 1-month old mice. Administration of a single dose of melatonin (10 mg/kg body weight) and ascorbic acid (10 mg/kg body weight) intraperitoneally for three consecutive days decreases the carbonyl content in 1- and 18-month-old mice significantly. The present study thus suggests that the formation of protein carbonyls in the cerebral hemispheres of the aging mice can be prevented by the antioxidative effects of melatonin and ascorbic acid that could in turn be beneficial in having health benefits from age-related neurodegenerative diseases.

  2. Engineered Trx2p industrial yeast strain protects glycolysis and fermentation proteins from oxidative carbonylation during biomass propagation

    Directory of Open Access Journals (Sweden)

    Gómez-Pastor Rocío

    2012-01-01

    Full Text Available Abstract Background In the yeast biomass production process, protein carbonylation has severe adverse effects since it diminishes biomass yield and profitability of industrial production plants. However, this significant detriment of yeast performance can be alleviated by increasing thioredoxins levels. Thioredoxins are important antioxidant defenses implicated in many functions in cells, and their primordial functions include scavenging of reactive oxygen species that produce dramatic and irreversible alterations such as protein carbonylation. Results In this work we have found several proteins specifically protected by yeast Thioredoxin 2 (Trx2p. Bidimensional electrophoresis and carbonylated protein identification from TRX-deficient and TRX-overexpressing cells revealed that glycolysis and fermentation-related proteins are specific targets of Trx2p protection. Indeed, the TRX2 overexpressing strain presented increased activity of the central carbon metabolism enzymes. Interestingly, Trx2p specifically preserved alcohol dehydrogenase I (Adh1p from carbonylation, decreased oligomer aggregates and increased its enzymatic activity. Conclusions The identified proteins suggest that the fermentative capacity detriment observed under industrial conditions in T73 wine commercial strain results from the oxidative carbonylation of specific glycolytic and fermentation enzymes. Indeed, increased thioredoxin levels enhance the performance of key fermentation enzymes such as Adh1p, which consequently increases fermentative capacity.

  3. Enhanced microwave absorbing properties and heat resistance of carbonyl iron by electroless plating Co

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongyu, E-mail: wanghongyu07010310@163.com; Zhu, Dongmei; Zhou, Wancheng; Luo, Fa

    2015-11-01

    Co coated carbonyl iron particles (Co (CI)) are fabricated through electroless plating method, and the electromagnetic microwave absorbing properties are investigated in the frequencies during 8.2–12.4 GHz. The complex permittivity of CI particles after electroless plating Co is higher than that of raw CI particles due to improvment of the polarization process. Furthermore, according to the XRD and TG results, the Co layer can enhance the heat resistance of CI particles. The bandwidth below −10 dB can reach 3.9 GHz for the Co(CI) absorbent. The results indicate that the electroless plating Co not only enhances the absorbing properties but also improves the heat resistance of CI. - Highlights: • The Co-coated carbonyl iron Co(CI) particles were prepared by electroless plating. • The electromagnetic wave absorbing properties of Co(CI) particles were studied. • The heat treatment on the absorbing property of Co(CI) particles was studied. • The Co(CI) particles have good absorbing property when compared with CI.

  4. Determination of carbonyl compounds (acetaldehyde and formaldehyde in polyethylene terephthalate containers designated for water conservation

    Directory of Open Access Journals (Sweden)

    Redžepović Azra S.

    2012-01-01

    Full Text Available Polyethylene terephthalate (PET has in the last several years become the main packaging material for many food products, particularly carbonated beverages and bottled water, as well as for products of chemical industry (packaging of various hygiene maintenance agents, pesticides, solvents, etc.. The strength and permeability properties of PET are very good for packaging of beverages, its resistance to chemicals is high and it has a high degree of transparency. Acetaldehyde and formaldehyde are formed during the thermoforming of PET containers. After cooling, acetaldehyde and formaldehyde remain trapped in the walls of a PET bottle and may migrate into the water after filling and storage. Since there are no migration tests in Serbia prescribed for the determination of acetaldehyde and formaldehyde, the purpose of the paper is to test the quantitative contents of carbonyl compounds (acetaldehyde and formaldehyde in PET containers of different volumes, made by various manufacturers of bottled mineral carbonated and noncarbonated water, and exposed to different temperatures. In this study, the migration of acetaldehyde and formaldehyde from PET bottles into mineral carbonated and noncarbonated water was determined by high performance liquid chromatography. Taking into consideration that formaldehyde and acetaldehyde have no UV active or fluorescent group, the chromatography shall be preceded by derivatization in a closed system (due to a low boiling point of acetaldehyde and formaldehyde, which shall transform carbonyl compounds into UV active compounds.

  5. Behavior of VOCs and carbonyl compounds emission from different types of wallpapers in Korea.

    Science.gov (United States)

    Lim, Jungyun; Kim, Suejin; Kim, Arong; Lee, Wooseok; Han, Jinseok; Cha, Jun-Seok

    2014-04-17

    Emissions of volatile organic compounds (VOCs) and carbonyls from three types of commercially available wallpapers (i.e., PVC-coated, paper-backed, natural material-coated) in Korea were evaluated using a 20 L small chamber. A total of 332 products were tested for emission factors, frequencies of occurrence and composition ratios. Toluene and formaldehyde concentrations were below Korean standard values for all products; however, the total VOC (TVOC) concentrations exceeded current standards (4.0 mg/m²·h) for 30 products. The TVOC emission factor for PVC-coated wallpapers, for which polymer materials are used in the manufacturing process, was seven and 16 times higher than those of paper-backed and natural material-coated wallpapers, respectively. The detection frequencies for toluene and formaldehyde were the highest (82.5%) and fourth highest (79.5%), respectively among the 50 target chemical species. The composition ratios for BTEX ranged from 0.3% to 5.1% and unidentified VOCs, which were not qualitatively analyzed using standard gas methods, ranged from 90.2% to 94.8%. Among six carbonyl compounds (acrolein was not detected in any type of wallpaper), acetone had the highest concentrations in PVC-coated (44.6%) and paper-backed (66.6%) wallpapers. Formaldehyde emissions were highest (64.6%) for natural material-coated wallpapers, a result of the formaldehyde-based resin used in the manufacturing process for these products.

  6. Analysis of the carbonyl group stretching vibrations in some structural fragments of poly-3-hydroxybutyrate

    CERN Document Server

    Pitsevich, George A; Doroshenko, Iryna

    2016-01-01

    The structure and the medium effects exerted on the spectral characteristics of the carbonyl group stretching vibrations in some structural fragments of poly-3-hydroxybutyrate have been analyzed. Calculations of the equilibrium configurations and IR spectra were carried out using the Gaussian program set in the approximation B3LYP/cc-pVDZ. It has been shown that typical bending of the poly-3-hydroxybutyrate chain is observed with an increase in the number of structural units. In order to explain the difference between the calculated and experimental frequencies of the C=O group stretching vibrations, the calculations of the potential energy curve associated with variations in the length of C=O bond and the subsequent numerical solution of a one-dimensional vibrational Schr\\"odinger equation have been performed. The medium effects have been taken into account within the scope of a polarizable continuum model. Owing to the inclusion of the above-mentioned factors, which affect frequencies of the carbonyl groups...

  7. Comparative Proteomic Analysis of Carbonylated Proteins from the Striatum and Cortex of Pesticide-Treated Mice

    Science.gov (United States)

    Coughlan, Christina; Walker, Douglas I.; Lohr, Kelly M.; Richardson, Jason R.; Saba, Laura M.; Caudle, W. Michael; Fritz, Kristofer S.; Roede, James R.

    2015-01-01

    Epidemiological studies indicate exposures to the herbicide paraquat (PQ) and fungicide maneb (MB) are associated with increased risk of Parkinson's disease (PD). Oxidative stress appears to be a premier mechanism that underlies damage to the nigrostriatal dopamine system in PD and pesticide exposure. Enhanced oxidative stress leads to lipid peroxidation and production of reactive aldehydes; therefore, we conducted proteomic analyses to identify carbonylated proteins in the striatum and cortex of pesticide-treated mice in order to elucidate possible mechanisms of toxicity. Male C57BL/6J mice were treated biweekly for 6 weeks with saline, PQ (10 mg/kg), MB (30 mg/kg), or the combination of PQ and MB (PQMB). Treatments resulted in significant behavioral alterations in all treated mice and depleted striatal dopamine in PQMB mice. Distinct differences in 4-hydroxynonenal-modified proteins were observed in the striatum and cortex. Proteomic analyses identified carbonylated proteins and peptides from the cortex and striatum, and pathway analyses revealed significant enrichment in a variety of KEGG pathways. Further analysis showed enrichment in proteins of the actin cytoskeleton in treated samples, but not in saline controls. These data indicate that treatment-related effects on cytoskeletal proteins could alter proper synaptic function, thereby resulting in impaired neuronal function and even neurodegeneration. PMID:26345149

  8. Impact of silica-coating on the microwave absorption properties of carbonyl iron powder

    Energy Technology Data Exchange (ETDEWEB)

    Li, J. [School of Science, Lanzhou University of Technology, Lanzhou, Gansu 730050 (China); Feng, W.J., E-mail: wjfeng@lut.cn [State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metal, Lanzhou University of Technology, Lanzhou 730050 (China); School of Science, Lanzhou University of Technology, Lanzhou, Gansu 730050 (China); Wang, J.S.; Zhao, X.; Zheng, W.Q. [School of Science, Lanzhou University of Technology, Lanzhou, Gansu 730050 (China); Yang, H. [State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metal, Lanzhou University of Technology, Lanzhou 730050 (China); School of Science, Lanzhou University of Technology, Lanzhou, Gansu 730050 (China)

    2015-11-01

    Microwave absorption properties, especially the band width and depth of reflection loss are highlighted as key measurement in studies of microwave absorber. In order to improve the band width and depth of reflection loss of carbonyl iron powder (CIP), we prepared SiO{sub 2} layers on the surface of CIP by using tetraethyl orthosilicate (TEOS) as a SiO{sub 2} source and 3-aminopropyl triethoxysilane (APTES) as a surface modifier. SiO{sub 2} layer was formed by the hydrolysis of TEOS. The results show that after treatment the CIP is covered by a 5–10 nm coating layer. Contrast to uncoated samples, coated samples show improved absorption properties. The minimum of reflection loss is −38.8 dB at 11 GHz and the band width of reflection loss exceeding −10 dB is from 8 GHz to 14 GHz. - Highlights: • Silica coatings were prepared on the surface of carbonyl iron powder. • Coating layers were identified by several ways. • We discussed the absorbing mechanism of coated samples. • Reflection loss was significantly improved, the width of RL exceeding −10 dB is from 8 GHz to 14 GHz.

  9. Penicitroamide, an Antimicrobial Metabolite with High Carbonylization from the Endophytic Fungus Penicillium sp. (NO. 24

    Directory of Open Access Journals (Sweden)

    Zi-Wei Feng

    2016-10-01

    Full Text Available Penicitroamide (1, a new metabolite with a new framework, was isolated from the ethyl acetate extract of the PDB (Potato Dextrose Broth medium of Penicillium sp. (NO. 24. The endophytic fungus Penicillium sp. (NO. 24 was obtained from the healthy leaves of Tapiscia sinensis Oliv. The structure of penicitroamide (1 features a bicyclo[3.2.1]octane core unit with a high degree of carbonylization (four carbonyl groups and one enol group. The chemical structure of penicitroamide (1 was elucidated by analysis of 1D-, 2D-NMR and MS data. In bioassays, penicitroamide (1 displayed antibacterial potency against two plant pathogens, Erwinia carotovora subsp. Carotovora (Jones Bersey, et al. and Sclerotium rolfsii Sacc. with MIC50 at 45 and 50 μg/mL. Compound 1 also showed 60% lethality against brine shrimp at 10 μg/mL. Penicitroamide (1 exhibited no significant activity against A549, Caski, HepG2 and MCF-7 cells with IC50 > 50 μg/mL. Finally, the possible biosynthetic pathway of penicitroamide (1 was discussed.

  10. Comparative Proteomic Analysis of Carbonylated Proteins from the Striatum and Cortex of Pesticide-Treated Mice

    Directory of Open Access Journals (Sweden)

    Christina Coughlan

    2015-01-01

    Full Text Available Epidemiological studies indicate exposures to the herbicide paraquat (PQ and fungicide maneb (MB are associated with increased risk of Parkinson’s disease (PD. Oxidative stress appears to be a premier mechanism that underlies damage to the nigrostriatal dopamine system in PD and pesticide exposure. Enhanced oxidative stress leads to lipid peroxidation and production of reactive aldehydes; therefore, we conducted proteomic analyses to identify carbonylated proteins in the striatum and cortex of pesticide-treated mice in order to elucidate possible mechanisms of toxicity. Male C57BL/6J mice were treated biweekly for 6 weeks with saline, PQ (10 mg/kg, MB (30 mg/kg, or the combination of PQ and MB (PQMB. Treatments resulted in significant behavioral alterations in all treated mice and depleted striatal dopamine in PQMB mice. Distinct differences in 4-hydroxynonenal-modified proteins were observed in the striatum and cortex. Proteomic analyses identified carbonylated proteins and peptides from the cortex and striatum, and pathway analyses revealed significant enrichment in a variety of KEGG pathways. Further analysis showed enrichment in proteins of the actin cytoskeleton in treated samples, but not in saline controls. These data indicate that treatment-related effects on cytoskeletal proteins could alter proper synaptic function, thereby resulting in impaired neuronal function and even neurodegeneration.

  11. Complex permeability and permittivity variation of carbonyl iron rubber in the frequency range of 2 to 18 GHz

    Directory of Open Access Journals (Sweden)

    Adriana Medeiros Gama

    2010-04-01

    Full Text Available The complex dielectric permittivity (e and magnetic permeability (m of Radar Absorbing Materials (RAM based on metallic magnetic particles (carbonyl iron particles embedded in a dielectric matrix (silicon rubber have been studied in the frequency range of 2 to 18 GHz. The relative permeability and permittivity of carbonyl iron-silicon composites for various mass fractions are measured by the transmission/reflection method using a vector network analyzer. The concentration dependence of permittivity and permeability on the frequency is analyzed. In a general way, the results show that e´ parameter shows a more significant variation among the evaluated parameters (e”, m”, m’. The comparison of dielectric and magnetic loss tangents (e”/e” and m”/m’, respectively shows more clearly the variation of both parameters (e and m according to the frequency. It is also observed that higher carbonyl iron content fractions favor both dielectric and magnetic loss tangents.

  12. Model of In Situ Composite of Cobalt(Ⅱ)-Phthalocyanine and Carbonyl Iron for Organic/Inorganic Nanocomposites

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Cobalt-phthalocyanine/iron nanocomposite particles have been obtained using method of composite in situ,with the mixture of carbonyl iron and solution of cobalt(Ⅱ)-phthalocyanine (Co-Pc) ultrasonic dispersing in N,N-dimethyl-formamide (DMF).Structure characterization of their inner and surface have relation with method of carbonyl iron joined in the mixture,contents of carbonyl iron and Co-Pc in the mixture of Co-Pc ultrasonic dispersing in DMF.With a method of composite in situ controlling reasonable experiment condition,it can be obtained that cobalt-phthalocyanine/iron nanocomposite particles has completely been covered with Co-Pc,they had structure of Chinese gooseberry in inner and mere made up of almost regular spherical shape and the average diameter is 1.4 μm.

  13. Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles

    Science.gov (United States)

    Hattori, Shohei; Kamezaki, Kazuki; Ogawa, Takahiro; Toyoda, Sakae; Katayama, Yoko; Yoshida, Naohiro

    2016-04-01

    Carbonyl sulfide (OCS or COS) is the most abundant gas containing sulfur in the atmosphere, with an average mixing ratio of 500 p.p.t.v. in the troposphere. OCS is suggested as a sulfur source of the stratospheric sulfate aerosols (SSA) which plays an important role in Earth's radiation budget and ozone depletion. Therefore, OCS budget should be validated for prediction of climate change, but the global OCS budget is imbalance. Recently we developed a promising new analytical method for measuring the stable sulfur isotopic compositions of OCS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ (Hattori et al., 2015). The first measurement of the δ34S value for atmospheric OCS coupled with isotopic fractionation for OCS sink reactions in the stratosphere (Hattori et al., 2011; Schmidt et al., 2012; Hattori et al., 2012) explains the reported δ34S value for background stratospheric sulfate, suggesting that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. This new method measuring δ34S values of OCS can be used to investigate OCS sources and sinks in the troposphere to better understand its cycle. It is known that some microorganisms in soil can degrade OCS, but the mechanism and the contribution to the OCS in the air are still uncertain. In order to determine sulfur isotopic enrichment factor of OCS during degradation via microorganisms, incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia and Cupriavidus, isolated from natural soil environments (Kato et al., 2008). As a result, sulfur isotope ratios of OCS were increased during degradation of OCS, indicating that reaction for OC32S is faster than that for OC33S and OC34S. OCS degradation via microorganisms is not mass-independent fractionation (MIF) process, suggesting that this

  14. Methane to acetic acid over Cu-exchanged zeolites: mechanistic insights from a site-specific carbonylation reaction.

    Science.gov (United States)

    Narsimhan, Karthik; Michaelis, Vladimir K; Mathies, Guinevere; Gunther, William R; Griffin, Robert G; Román-Leshkov, Yuriy

    2015-02-11

    The selective low temperature oxidation of methane is an attractive yet challenging pathway to convert abundant natural gas into value added chemicals. Copper-exchanged ZSM-5 and mordenite (MOR) zeolites have received attention due to their ability to oxidize methane into methanol using molecular oxygen. In this work, the conversion of methane into acetic acid is demonstrated using Cu-MOR by coupling oxidation with carbonylation reactions. The carbonylation reaction, known to occur predominantly in the 8-membered ring (8MR) pockets of MOR, is used as a site-specific probe to gain insight into important mechanistic differences existing between Cu-MOR and Cu-ZSM-5 during methane oxidation. For the tandem reaction sequence, Cu-MOR generated drastically higher amounts of acetic acid when compared to Cu-ZSM-5 (22 vs 4 μmol/g). Preferential titration with sodium showed a direct correlation between the number of acid sites in the 8MR pockets in MOR and acetic acid yield, indicating that methoxy species present in the MOR side pockets undergo carbonylation. Coupled spectroscopic and reactivity measurements were used to identify the genesis of the oxidation sites and to validate the migration of methoxy species from the oxidation site to the carbonylation site. Our results indicate that the Cu(II)-O-Cu(II) sites previously associated with methane oxidation in both Cu-MOR and Cu-ZSM-5 are oxidation active but carbonylation inactive. In turn, combined UV-vis and EPR spectroscopic studies showed that a novel Cu(2+) site is formed at Cu/Al <0.2 in MOR. These sites oxidize methane and promote the migration of the product to a Brønsted acid site in the 8MR to undergo carbonylation.

  15. Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

    Directory of Open Access Journals (Sweden)

    R. M. Healy

    2008-03-01

    Full Text Available A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NOx and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl-hydroxylamine (PFBHA to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively.

    Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous chemistry as a pathway for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.

  16. SnCl2/Cu-Mediated Carbonyl Allylation Reaction in Water:Scope,Selectivity and Mechanism

    Institute of Scientific and Technical Information of China (English)

    TAN,Xiang-Hui(谭翔晖); HOU,Yong-Quan(侯永泉); LIU,Lei(刘磊); GUO,Qing-Xiang(郭庆祥)

    2004-01-01

    Copper was found to be able to promote the SnC12-mediated carbonyl allylation reactions in water,giving the corresponding homoallylic alcohol products in very high yields.Detailed studies showed that the reaction could be applied to a variety of carbonyl compounds including those with hydroxyl,amino and nitro groups.It was also found that this reaction showed good regioselectivities for some substrates.Furthermore,carefully controled experiments and in situ NMR measurements provided important insights into the mechanism of the newly developed reaction.

  17. 1-Ethyl-3-methylimidazolium acetate as a highly efficient organocatalyst for cyanosilylation of carbonyl compounds with trimethylsilyl cyanide

    Science.gov (United States)

    Ullah, Bakhtar; Chen, Jingwen; Zhang, Zhiguo; Xing, Huabin; Yang, Qiwei; Bao, Zongbi; Ren, Qilong

    2017-01-01

    1-Ethyl-3-methylimidazolium acetate is introduced as a robust organocatalyst for solvent-free cyanosilylation of carbonyl compounds with trimethylsilyl cyanide (TMSCN). The catalyst loading can be reduced to as low as 0.1–0.0001 mol % under mild reaction conditions, giving considerably high TOF values from 10,843 h−1 to 10,602,410 h−1 in the field of organocatalyzed transformations. The present protocol not only tolerates with extensive carbonyl compounds but also provides somewhat insight into the mechanism of ionic liquids (ILs)-catalyzed reactions. PMID:28198462

  18. Determination of gaseous and particulate carbonyls (glycolaldehyde, hydroxyacetone, glyoxal, methylglyoxal, nonanal and decanal) in the atmosphere at Mt. Tai

    Science.gov (United States)

    Kawamura, K.; Okuzawa, K.; Aggarwal, S. G.; Irie, H.; Kanaya, Y.; Wang, Z.

    2013-05-01

    Gaseous and particulate semi-volatile carbonyl compounds were determined every three hours in the atmosphere of Mount Tai (elevation, 1534 m) in the North China Plain during 2-5, 23-24 and 25 June 2006 under clear sky conditions. Using a two-step filter cartridge in a series, particulate carbonyls were first collected on a quartz filter and then gaseous carbonyls were collected on a quartz filter impregnated with O-benzylhydroxylamine (BHA). After the two-step derivatization with BHA and N,O-Bis(trimethylsilyl)trifluoroacetamide (BSTFA), carbonyl derivatives were measured using a gas chromatography. The gaseous concentrations were obtained as follow: glycolaldehyde (range 0-826 ng m-3, average 303 ng m-3), hydroxyacetone (0-579 ng m-3, 126 ng m-3), glyoxal (46-1200 ng m-3, 487 ng m-3), methylglyoxal (88-2690 ng m-3, 967 ng m-3), n-nonanal (0-500 ng m-3, 89 ng m-3), and n-decanal (0-230 ng m-3, 39 ng m-3). These concentrations are among the highest ever reported in the urban and forest atmosphere. We found that gaseous α-dicarbonyls (glyoxal and methylglyoxal) are more than 20 times more abundant than particulate carbonyls and that glycolaldehyde is one order of magnitude more abundant than in aerosol phase. In contrast, hydroxyacetone and normal aldehydes (nonanal and decanal) are equally present in both phases. Time-resolved variations of carbonyls did not show any a clear diurnal pattern, except for hydroxyacetone. We found that glyoxal, methylglyoxal and glycolaldehyde positively correlated with levoglucosan (a tracer of biomass burning), suggesting that a contribution from field burning of agricultural wastes (wheat crops) is significant for the bifunctional carbonyls in the atmosphere of Mt. Tai. Upward transport of the pollutants to the mountaintop from the low lands in the North China Plain is a major process to control the distributions of carbonyls in the upper atmosphere over Mt. Tai.

  19. Contrasting Influence of NADPH and a NADPH-Regenerating System on the Metabolism of Carbonyl-Containing Compounds in Hepatic Microsomes

    Science.gov (United States)

    Carbonyl containing xenobiotics may be susceptible to NADPH-dependent cytochrome P450 (P450) and carbonyl-reduction reactions. In vitro hepatic microsome assays are routinely supplied NADPH either by direct addition of NADPH or via an NADPH-regenerating system (NRS). In contrast ...

  20. [carbonyl-C-11]desmethyl-WAY-100635 (DWAY) is a potent and selective radioligand for central 5-HT1A receptors in vitro and in vivo

    NARCIS (Netherlands)

    Pike, VW; Halldin, C; McCarron, JA; Lundkvist, C; Hirani, E; Olsson, H; Hume, SP; Karlsson, P; Osman, S; Swahn, CG; Hall, H; Wikstrom, H; Mensonidas, M; Poole, KG; Farde, L

    1998-01-01

    [carbonyl-C-11]Desmethyl-WAY-100635 (DWAY) is possibly a low-level metabolite appearing in plasma after intravenous administration of [carbonyl(11)C]WAY-100635 to human subjects for positron emission tomographic (PET) imaging of brain 5-HT1A receptors. In this study we set out to assess the ability

  1. Syntheses of fused tetrahydro--carboline analogues through imide carbonyl activation using BBr3: Evidence for the involvement of fused cyclic -acyliminium ion intermediate

    Indian Academy of Sciences (India)

    Selvaraj Mangalaraj; Jayaraman Selvakumar; Chinnasamy Ramaraj Ramanathan

    2015-05-01

    The fused cyclic -acyliminium ion generated during the imide carbonyl activation reaction of phenethylphthalimide was confirmed by single crystal X-ray diffraction. The Lewis acid assisted imide carbonyl activation methodology was successfully extended to synthesize fused tetrahydro--carboline units from the corresponding -indolylethylimides.

  2. Stepwise construction of manganese-chromium carbonyl chalcogenide complexes: synthesis, electrochemical properties, and computational studies.

    Science.gov (United States)

    Shieh, Minghuey; Miu, Chia-Yeh; Huang, Kuo-Chih; Lee, Chung-Feng; Chen, Bao-Gun

    2011-08-15

    When trigonal-bipyramidal clusters, [PPN][E(2)Mn(3)(CO)(9)] (E = S, Se), were treated with Cr(CO)(6) and PPNCl in a molar ratio of 1:1:2 or 1:2:2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)(5)-incorporated HE(2)Mn(3)-complexes [PPN](2)[HE(2)Mn(3)Cr(CO)(14)] (E = S, [PPN](2)[1a]; Se, [PPN](2)[1b]), respectively, were formed. X-ray crystallographic analysis showed that 1a and 1b were isostructural and each displayed an E(2)Mn(3) square-pyramidal core with one of the two basal E atoms externally coordinated with one Cr(CO)(5) group and one Mn-Mn bond bridged by one hydrogen atom. However, when the TMBA(+) salts for [E(2)Mn(3)(CO)(9)](-) were mixed with Cr(CO)(6) in a molar ratio of 1:1 in 4 M KOH/MeOH solutions and refluxed at 60 °C, mono-Cr(CO)(3)-incorporated E(2)Mn(3)Cr octahedral clusters [TMBA](3)[E(2)Mn(3)Cr(CO)(12)] (E = S, [TMBA](3)[2a]; Se, [TMBA](3)[2b]), respectively, were obtained. Clusters 2a and 2b were isostructural, and each consisted of an octahedral E(2)Mn(3)Cr core, in which each Mn-Mn or Mn-Cr bond of the Mn(3)Cr plane was semibridged by one carbonyl ligand. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 °C. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)(5)-incorporated HE(2)Mn(3)-clusters [HE(2)Mn(3)Cr(2)(CO)(19)](2-) (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)(6) heated in refluxing CH(2)Cl(2). Clusters 3a and 3b were structurally related to clusters 1a and 1b, but with the other bare E atom (E = S, 3a; Se, 3b) further externally coordinated with one Cr(CO)(5) group. The nature, cluster transformation, and electrochemical properties of the mixed manganese-chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton with the aid of molecular calculations at the BP86 level of the

  3. Carbonyl Diisocyanate CO(NCO)2: Synthesis and Structures in Solid State and Gas Phase.

    Science.gov (United States)

    Klapötke, Thomas M; Krumm, Burkhard; Rest, Sebastian; Scharf, Regina; Schwabedissen, Jan; Stammler, Hans-Georg; Mitzel, Norbert W

    2016-07-01

    A modified synthesis for carbonyl diisocyanate, CO(NCO)2, starting from trichloroisocyanuric acid and diphosgene is described. In addition to the previously reported (13)C NMR resonances, the (15)N NMR shift is determined for the first time. The structure in the solid state was determined by X-ray diffraction (XRD) on in situ grown crystals, that in the gas phase was experimentally determined by electron diffraction (GED) and for single molecules theoretically by quantum-chemical calculations. The structures are compared and discussed with related systems. Quantum-chemical calculations as well as GED and XRD prove syn-syn to be the conformation of lowest energy. In quantum-chemical calculations and GED the presence of a syn-anti conformer was confirmed and the structure of this conformer was determined.

  4. Investigation on peak frequency of the microwave absorption for carbonyl iron/epoxy resin composite

    Energy Technology Data Exchange (ETDEWEB)

    Wang Bochong; Wei Jianqiang; Yang Yong; Wang Tao [Institute of Applied Magnetics, Key Laboratory of Magnetism and Magnetic Materials of Ministry of Education, Lanzhou University, Lanzhou 730000 (China); Li Fashen, E-mail: lifs@lzu.edu.c [Institute of Applied Magnetics, Key Laboratory of Magnetism and Magnetic Materials of Ministry of Education, Lanzhou University, Lanzhou 730000 (China)

    2011-04-15

    Microwave absorbing characteristics of carbonyl iron/epoxy resin composite with various volume concentrations were investigated in 0.1-18 GHz. According to the electromagnetic parameters and thicknesses of the sample, numerical calculation and experiment have demonstrated that the frequency dependence of the microwave absorption comply with the quarter-wavelength ({lambda}/4) matching model that may explain not only the peak frequency but also the number of the peaks. It implies that the quarter-wavelength condition can be successfully applied to understand and predict the peak frequency of the microwave absorption for ferromagnetic metal-based composites. - Research highlights: > The dip in RL complies with the quarter-wavelength condition. > Two dips appear simultaneously when the sample thickness is thicker than the critical thickness t{sub c}{sup 3/4}. > The peak frequency of the dips can be manipulated by changing the sample thickness.

  5. Detection of Protein Carbonyls by Means of Biotin Hydrazide-Streptavidin Affinity Methods.

    Science.gov (United States)

    Hensley, Kenneth

    2015-01-01

    Oxidative posttranslational protein modifications occur as a normal process of cell biology and to a greater extent during pathogenic conditions. The detection and quantitation of protein oxidation has posed a continuing challenge to bioanalytical chemists because of the following reasons: The products of oxidative protein damage are chemically diverse; protein oxidation generally occurs at low background levels; and the complexity of biological samples introduces high background noise when standard techniques such as immunolabeling are applied to "dirty" tissue extracts containing endogenous immunoglobulins or small molecular weight, chemically reactive compounds has been developed which circumvents these difficulties by incorporating a biotin label at sites of protein carbonylation. Biotin hydrazide-labeled proteins are detectable using standard streptavidin-coupled detection techniques such as peroxidase-catalyzed chemiluminescence of immunoblots. Advantages of the biotin hydrazide-labeling technique are its sensitivity and its lack of reliance upon antibodies that inevitably suffer from nonspecific background noise and contaminating endogenous immunoglobulins.

  6. Synthesis of high refractive spiro heterocyclic derivatives through thioacetalization of multi-carbonyl compounds

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Jim Young; Maheswara, Muchchintala; Do, Jung Yun [Pusan National Univ., Busan (Korea, Republic of)

    2012-04-15

    Preparation of several new spirocyclic mercaptol derivatives is described. Thiol protection on multi-carbonyl compounds allows of high sulfur content necessary to induce high refractive index. Condensation of 1,3-dimercapto-2-propanol and cyclohexanone followed by successive oxidation and thioacetalization affords a dispiro cycle with four sulfurs. Selective S,S-protection of cyclohexane-1,4-dione is achieved with 1,3-dimercapto-2-propanol and 2,3-dimercapto-1-propanol to provide dispiro cycles with four sulfurs. Olefineoxidation of norbornene gives a useful dialdehyde intermediate which is transformed to 1,3-dithiolane for a linearly-bound-cyclic molecule. Refractive index of linearly-bound-cycles was below 1.60 and dispiro cycles exhibited high refractive index of 1.57-1.69.

  7. Pomegranate phenolics inhibit formation of advanced glycation endproducts by scavenging reactive carbonyl species.

    Science.gov (United States)

    Liu, Weixi; Ma, Hang; Frost, Leslie; Yuan, Tao; Dain, Joel A; Seeram, Navindra P

    2014-11-01

    Advanced Glycation Endproducts (AGEs) are a heterogeneous group of molecules produced from non-enzymatic glycation. Accumulation of AGEs in vivo plays an important role in the pathology of chronic human diseases including type-2 diabetes and Alzheimer's disease. Natural AGEs inhibitors such as the pomegranate (Punica granatum) fruit show great potential for the management of these diseases. Herein, we investigated the in vitro anti-glycation effects of a pomegranate fruit extract (PE), its phenolic constituents [punicalagin (PA), ellagic acid (EA) and gallic acid (GA)], and their in vivo derived colonic metabolites [urolithin A (UA) and urolithin B (UB)]. All of the samples showed anti-glycation activities and PE, PA, and EA were more potent inhibitors than the positive control, aminoguanidine. PE and the purified phenolics also exhibited carbonyl scavenger reactivity. Our study suggests that pomegranate may offer an attractive dietary strategy for the prevention and treatment of AGE-related diseases such as type-2 diabetes and Alzheimer's disease.

  8. Protonation Sites, Tandem Mass Spectrometry and Computational Calculations of o-Carbonyl Carbazolequinone Derivatives

    Science.gov (United States)

    Martínez-Cifuentes, Maximiliano; Clavijo-Allancan, Graciela; Zuñiga-Hormazabal, Pamela; Aranda, Braulio; Barriga, Andrés; Weiss-López, Boris; Araya-Maturana, Ramiro

    2016-01-01

    A series of a new type of tetracyclic carbazolequinones incorporating a carbonyl group at the ortho position relative to the quinone moiety was synthesized and analyzed by tandem electrospray ionization mass spectrometry (ESI/MS-MS), using Collision-Induced Dissociation (CID) to dissociate the protonated species. Theoretical parameters such as molecular electrostatic potential (MEP), local Fukui functions and local Parr function for electrophilic attack as well as proton affinity (PA) and gas phase basicity (GB), were used to explain the preferred protonation sites. Transition states of some main fragmentation routes were obtained and the energies calculated at density functional theory (DFT) B3LYP level were compared with the obtained by ab initio quadratic configuration interaction with single and double excitation (QCISD). The results are in accordance with the observed distribution of ions. The nature of the substituents in the aromatic ring has a notable impact on the fragmentation routes of the molecules. PMID:27399676

  9. Gold/Iron Carbonyl Clusters for Tailored Au/FeOx Supported Catalysts

    Directory of Open Access Journals (Sweden)

    Stefania Albonetti

    2011-12-01

    Full Text Available A novel preparation method was developed for the preparation of gold/iron oxide supported catalysts using the bimetallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO16] and [NEt4][AuFe4(CO16] as precursors of highly dispersed nanoparticles over different supports. A series of catalysts with different metal loadings were prepared and tested in the complete oxidation of dichlorobenzene, toluene, methanol and in the preferential oxidation of CO in the presence of H2 (PROX as model reactions. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS point out the way the nature of the precursors and the thermal treatment conditions affected the dispersion of the active phase and their catalytic activity in the studied reactions.

  10. Temporal variation of carbonyl compound concentrations at a semi-rural site in Denmark

    DEFF Research Database (Denmark)

    Christensen, C.S.; Skov, H.; Nielsen, T.

    2000-01-01

    The atmospheric concentrations of formaldehyde, acetaldehyde and acetone were measured by the DNPH-technique at the semi-rural site Lille Valby, Denmark (55 degrees N) between May-July 1995, The average concentrations were observed to be 1.2 ppbv for formaldehyde, 0.8 ppbv for acetaldehyde and 1.......9 ppbv for acetone, For the set of carbonyl compounds, concentrations were found to be highly correlated, though only during daytime, The weak correlations observed during nighttime are believed to be caused by the dry deposition of especially formaldehyde, During periods with low photochemical activity...... of hydrocarbons during long-range transport. Especially, the concentration levels of acetone showed a pronounced seasonal-variation with the highest levels observed during summertime and lowest in winter and spring. The seasonal variation in the concentration levels of formaldehyde and acetaldehyde were small...

  11. Magnetorheology of suspensions based on graphene oxide coated or added carbonyl iron microspheres and sunflower oil

    Science.gov (United States)

    Chen, Kaikai; Zhang, Wen Ling; Shan, Lei; Zhang, Xiangjun; Meng, Yonggang; Choi, Hyoung Jin; Tian, Yu

    2014-10-01

    Magnetorheological (MR) fluids based on carbonyl iron (CI) particles coated with graphene oxide (GO) and sunflower oils were studied and compared with MR fluids (MRFs) prepared with CI particles added with GO sheets. Adding GO sheets into CI had a negligible effect on the rheological properties of the MRF. Coating the spheres with GO markedly decreased the shear strength at high shear rates due to the remarkable lubricating function of the GO surface. Different behaviors were observed in the shear thickening phenomenon when the GO surface changed the mechanical interaction between particles. The results demonstrated the importance of the role of interparticle friction for MRF in shear mode and discussed the weak shear thickening phenomenon with fine lubricating coating layers and oils.

  12. Synthesis of Unsymmetric Ureas by Selenium-Catalyzed Oxidative-Reductive Carbonylation with CO

    Institute of Scientific and Technical Information of China (English)

    MEI Jian-Ting; LU Shi-Wei

    2003-01-01

    @@ Unsymmetric, substituted ureas that contain the peptide bond (NHCONH), many of which possess biological activities, are widely used as herbicides, agrochemicals and pharmaceuticals. [1,2] A series of unsymmetric ureascontaining substituted groups have been synthesized via selenium-catalyzed selective oxidative-reductive carbonylation of amines and nitro compounds with CO instead of phosgene in one-pot reaction. [3,4] These catalytic reactions are important from both synthetic and industrial points of view, because not only the reactions can be proceeded with high selectivity of higher than 99% towards desired unsymmetric ureas, but also there exists a phase-transfer process of the selenium catalyst in thereaction, so that the after-treatment of the catalysts and products from the reaction systems can be easily separated by simple phase separation.

  13. Simple and fully automated preparation of [carbonyl-{sup 11}C]WAY-100635

    Energy Technology Data Exchange (ETDEWEB)

    Wadsak, W.; Ettlinger, D.E; Dudczak, R.; Kletter, K. [Medical Univ. of Vienna (Austria). Dept. of Nuclear Medicine; Mien, L.K. [Medical Univ. of Vienna (Austria). Dept. of Nuclear Medicine; Medical Univ. of Vienna (Austria). Dept. of Psychiatry; Vienna Univ. (Austria). Dept. of Pharmaceutical Technology and Biopharmaceutics; Lanzenberger, R.R. [Medical Univ. of Vienna (Austria). Dept. of Psychiatry; Haeusler, D. [Medical Univ. of Vienna (Austria). Dept. of Nuclear Medicine; Vienna Univ. (Austria). Dept. of Pharmaceutical Technology and Biopharmaceutics; Mitterhauser, M. [Medical Univ. of Vienna (Austria). Dept. of Nuclear Medicine; Vienna Univ. (Austria). Dept. of Pharmaceutical Technology and Biopharmaceutics; General Hospital of Vienna (Austria). Hospital Pharmacy

    2007-07-01

    So far, [carbonyl-{sup 11}C]WAY-100635 is the PET-tracer of choice for 5HT{sub 1A}-receptor-imaging. Since the preparation is still a challenge, we aimed at (1) the evaluation of various essential parameters for the successful preparation, (2) the simplification of the radiosynthesis and (3) the establishment of a safe and fully automated system. The preparation is based on a commercial synthesizer and all chemicals are used without further processing. We found a low failure rate (7.7%), high average yield (4.0 {+-} 1.0 GBq) and a specific radioactivity of 292 {+-} 168 GBq/{mu}mol (both at the end of synthesis, EOS). (orig.)

  14. Restoration of membrane potential in mitochondria deenergized with carbonyl cyanide p-trifluoromethoxyphenylhydrazone (FCCP).

    Science.gov (United States)

    Toninello, A; Siliprandi, N

    1982-11-15

    The membrane potential (delta psi) of rat liver mitochondria dropped upon addition of carbonyl cyanide p-trifluoromethoxyphenylhydrazone (FCCP) but was gradually and fully restored to the original value by the subsequent addition of dithioerythritol. Concomitantly, Ca2+ released from mitochondria was reaccumulated and the oxidative phosphorylation process completely recoupled. Neither of these effects has been observed with dinitro-o-cresol or 2,4-dinitrophenol, uncouplers which, unlike FCCP, do not react with thiols. Delta psi abolished by FCCP was also restored, though incompletely, by albumin; a prompt and complete restoration was however achieved upon subsequent addition of dithioerythritol. Dithioerythritol also completely and rapidly restored the delta psi decreased by addition of diazene dicarboxylic acid bisdimethylamide (diamide).

  15. The hydrogen bond stabilizing effect in enammonium salts of captodative aminoalkenes containing a carbonyl group

    Science.gov (United States)

    Fedorov, S. V.; Rulev, A. Yu; Chipanina, N. N.; Sherstyannikova, L. V.; Turchaninov, V. K.

    2004-03-01

    Enhanced stability of enammonium salts of captodative carbonyl-containing aminoalkenes as compared to the salts of simple enamines is discussed on the basis of 1H and 13C NMR, IR, UV spectroscopy and the results quantum chemical calculations. Stabilization of the N-protonated form of captodative aminoalkenes is due to either intramolecular (NH +⋯OC) or intermolecular (NH +⋯Solv or NH +⋯X -) hydrogen bonding, whereas the C-protonated form is destabilized due to umpolung of the carbon-carbon double bond. The formation of bifurcated (three-centered) hydrogen bond between the enammonium cation and the solvent is demonstrated. The three-centered solvate complex is characterized by nonclassical dependence of the chemical shift of the bridging hydrogen atom from the proton-acceptor power of the solvent.

  16. Carbonyl Vibrational Wave Packet Circulation in Mn$_2$(CO)$_{10}$ Driven by Ultrashort Polarized Laser Pulses

    CERN Document Server

    Abdel-Latif, Mahmoud K

    2011-01-01

    The excitation of the degenerate $E_1$ carbonyl stretching vibrations in dimanganese decacarbonyl is shown to trigger wave packet circulation in the subspace of these two modes. On the time scale of about 5 picoseconds intramolecular anharmonic couplings do not cause appreciable disturbance, even under conditions where the two $E_1$ modes are excited by up to about two vibrational quanta each. The compactness of the circulating wave packet is shown to depend strongly on the excitation conditions such as pulse duration and field strength. Numerical results for the solution of the seven-dimensional vibrational Schr\\"odinger equation are obtained for a density functional theory based potential energy surface and using the multi-configuration time-dependent Hartree method.

  17. Adiabatic mixed-field orientation of ground-state-selected carbonyl sulfide molecules

    CERN Document Server

    Kienitz, Jens S; Mullins, Terry; Długołęcki, Karol; González-Férez, Rosario; Küpper, Jochen

    2016-01-01

    We experimentally demonstrated strong adiabatic mixed-field orientation of carbonyl sulfide molecules (OCS) in their absolute ground state of $\\text{N}_{\\text{up}}/\\text{N}_{\\text{tot}}=0.882$. OCS was oriented in combined non-resonant laser and static electric fields inside a two-plate velocity map imaging spectrometer. The transition from non-adiabatic to adiabatic orientation for the rotational ground state was studied by varying the applied laser and static electric field. Above static electric field strengths of 10~kV/cm and laser intensities of $10^{11} \\text{W/cm}^2$ the observed degree of orientation reached a plateau. These results are in good agreement with computational solutions of the time-dependent Schr\\"odinger equation.

  18. XPCS study of dynamic correlation in polyurethane gel-carbonyl iron composite under magnetic field

    Energy Technology Data Exchange (ETDEWEB)

    Grigoriew, Helena [Institute of Nuclear Chemistry and Technology, Warsaw 03195 (Poland); Wiegart, Lutz [ESRF, Grenoble, 38043 Cedex 9 (France); Boczkowska, Anna [Faculty of Materials Science, Warsaw University of Technology (Poland); Mirkowska, Monika, E-mail: haga311@hotmail.co [Institute of Electronic Materials Technology, Warsaw (Poland)

    2010-10-01

    An X-ray photon correlation spectroscopy (XPCS) study of composite-type material consisting of polyurethane gel and carbonyl iron micrometric spheres was performed under magnetic fields of 0, 300 and 600 mT. The onion-like spheres structure was destroyed during the composite processing. The following conclusions were obtained from the study: -The polyurethane matrix is preferred as a source for the observed dynamic effects. -Below 300mT the material dynamics in direction of the outer magnetic field are very clear. -For 600 mT the dependence of the dynamics on magnetic field direction disappears, but the correlation rate is much higher. These findings may be caused by a disturbance of the polymer mesostructure by larger strain leading to its cross-linking.

  19. Magnetorheology of xanthan-gum-coated soft magnetic carbonyl iron microspheres and their polishing characteristics

    Science.gov (United States)

    Kwon, Seung Hyuk; Choi, Hyoung Jin; Lee, Jung Won; Hong, Kwang Pyo; Cho, Myeong Woo

    2013-06-01

    Magnetorheological (MR) fluids are colloidal suspensions of soft magnetic particles dispersed in a non-magnetic liquid. Among their applications, MR polishing has attracted considerable attention owing to its smart control of the polishing characteristics for dedicated microelectromechanical system applications. To improve the polishing characteristics of MR fluids, we fabricated carbonyl iron (CI) microspheres coated with xanthan gum (XG) by using a solvent casting method. The morphologies and densities of both pure CI and CI/XG particles were characterized using a scanning electron microscope and a pycnometer, respectively. In addition, the rheological characteristics of the MR fluids under various applied magnetic field strengths were examined using a rotational rheometer. The MR polishing characteristics were conducted using an MR polishing machine to examine the surface roughness and the material removal by MR polishing with added nano-ceria slurry abrasives.

  20. Study on Ni/C catalysts for vapor phase carbonylation of ethanol

    Institute of Scientific and Technical Information of China (English)

    Qing Zhang; Huifang Wang; Guosong Sun; Kelin Huang; Weiping Fang; Yiquan Yang

    2008-01-01

    Activated carbon-supported Ni catalysts for vapor phase carbonylation of ethanol to propionic acid in the presence of ethyl iodide as promoter were investigated. Under optimum reaction conditions, the conversions of carbon monoxide and ethanol were measured to be 81.4% and 98.4%, respectively, while the selectivity for propionic acid was found to be 98.65%. The catalyst was stable within 48 h on stream. XRD and XPS methods were used to characterize the structures and surface properties of the fresh and tested catalysts. The characterization results indicated that aggregation of nickel particles and formation of nickel iodide on the catalyst surface should be responsible for the deactivation of the catalysts.

  1. A highly efficient procedure for the oxathioacetalization of carbonyl compounds under solvent-free conditions

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The novel efficient procedure has been developed for the oxathioacetalization of carbonyl compounds and 2-mercaptoethanol using the novel carbon-based sulfonic acid as catalyst under solvent-free condition at room temperature. The results showed that the novel catalyst was very efficient for the reactions with good to excellent yields in short time. The novel catalyst owned many advantages such as operational simplicity,without need of any solvent,small amount of usage,low cost of the catalyst used,high yields,applicability to large-scale reactions,reusability and chemoselectivity over the traditional catalysts,which made the catalyst one of the best choices for the reactions.

  2. Carbonyl sulfide as an inverse tracer for biogenic organic carbon in gas and aerosol phases

    Science.gov (United States)

    de Gouw, J. A.; Warneke, C.; Montzka, S. A.; Holloway, J. S.; Parrish, D. D.; Fehsenfeld, F. C.; Atlas, E. L.; Weber, R. J.; Flocke, F. M.

    2009-03-01

    Carbonyl sulfide (COS) is a long-lived trace gas in the atmosphere with an oceanic source and a surface sink through the uptake by vegetation and soils. We demonstrate the use of COS as an inverse tracer for the impact of biogenic emissions on an air mass including the formation of secondary organic aerosol (SOA). Using airborne data from the summer of 2004 over the northeastern U.S., we find that air masses with reduced COS in the continental boundary layer had on average higher mixing ratios of biogenic VOCs (isoprene, monoterpenes, methanol) and their photo-oxidation products (methacrolein, methyl vinyl ketone, methyl furan and MPAN, a peroxyacyl nitrate derived from isoprene). Measurements of water-soluble organic carbon were only weakly correlated with COS, indicating that SOA formation from biogenic precursors was a small contribution to the total.

  3. Field observations of carbonyl sulfide deficit near the ground: Possible implication of vegetation

    Science.gov (United States)

    Mihalopoulos, N.; Bonsang, B.; Nguyen, B. C.; Kanakidou, M.; Belviso, S.

    In order to study carbonyl sulfide sources and sinks at ground level, two experiments were conducted in 1986 during temperature inversion events. In the first experiment, the samples were collected in a coastal area during land-breeze events. In the second experiment, COS vertical profiles were carried out in an agricultural area, within and above an inversion layer near the ground. Both stable atmospheric situations resulted in a deficit of COS near the ground which is attributed to the existence of a sink of COS at this level. Deposition onto vegetation seems to be the most likely mechanism for this COS uptake, a conclusion in agreement with the results of laboratory and soil flux chambers experiments.

  4. Oxidative Carbonylation of Aromatic Amines with CO Catalyzed by 1,3-Dialkylimidazole-2-selenone in Ionic Liquids

    Directory of Open Access Journals (Sweden)

    Fengshou Tian

    2015-01-01

    Full Text Available 1,3-Dialkylimidazole-2-selenone as a novel substituted selenium heterocyclic catalyst was used to catalyze oxidative carbonylation of aromatic amines with carbon monoxide in the presence of air to symmetrical ureas in up to 97% yield in ionic liquids.

  5. Photoelectron velocity-map imaging and theoretical studies of heteronuclear metal carbonyls MNi(CO)3- (M = Mg, Ca, Al)

    Science.gov (United States)

    Xie, Hua; Zou, Jinghan; Yuan, Qinqin; Fan, Hongjun; Tang, Zichao; Jiang, Ling

    2016-03-01

    The heteronuclear metal carbonyl anions MNi(CO)3- (M = Mg, Ca, Al) have been investigated using photoelectron velocity-map imaging spectroscopy. Electron affinities of neutral MNi(CO)3 (M = Mg, Ca, Al) are measured from the photoelectron spectra to be 1.064 ± 0.063, 1.050 ± 0.064, and 1.541 ± 0.040 eV, respectively. The C-O stretching mode in these three clusters is observed and the vibrational frequency is determined to be 2049, 2000, and 2041 cm-1 for MgNi(CO)3, CaNi(CO)3, and AlNi(CO)3, respectively. Density functional theory calculations are carried out to elucidate the geometric and electronic structures and to aid the experimental assignments. It has been found that three terminal carbonyls are preferentially bonded to the nickel atom in these heterobinuclear nickel carbonyls MNi(CO)3-1/0, resulting in the formation of the Ni(CO)3 motif. Ni remains the 18-electron configuration for MgNi(CO)3 and CaNi(CO)3 neutrals, but not for AlNi(CO)3. This is different from the homobinuclear nickel carbonyl Ni-Ni(CO)3 with the involvement of three bridging ligands. Present findings would be helpful for understanding CO adsorption on alloy surfaces.

  6. [Hmim]3PW12O40: A high-efficient and green catalyst for the acetalization of carbonyl compounds

    Institute of Scientific and Technical Information of China (English)

    Yan; Lü

    2010-01-01

    [Hmim]3PW12O40 was developed and used in the acetalization of carbonyl compounds in excellent yields. The ionic liquid-heteropoly acid hybrid compound and reaction medium formed temperature-dependent phase-separation system with the ease of product as well as catalyst separation. The catalyst was recycled more than 10 times without any apparent loss of catalytic activity.

  7. Isotope effect in the carbonyl sulfide reaction with O(3P)

    DEFF Research Database (Denmark)

    Hattori, Shohei; Schmidt, Johan Albrecht; Mahler, Denise W.;

    2012-01-01

    The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O((3)P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear ...

  8. Determination and Comparison of Carbonyl Stretching Frequency of a Ketone in Its Ground State and the First Electronic Excited State

    Science.gov (United States)

    Bandyopadhyay, Subhajit; Roy, Saswata

    2014-01-01

    This paper describes an inexpensive experiment to determine the carbonyl stretching frequency of an organic keto compound in its ground state and first electronic excited state. The experiment is simple to execute, clarifies some of the fundamental concepts of spectroscopy, and is appropriate for a basic spectroscopy laboratory course. The…

  9. Protein hydroperoxides and carbonyl groups generated by porphyrin-induced photo-oxidation of bovine serum albumin

    DEFF Research Database (Denmark)

    Silvester, J A; Timmins, G S; Davies, Michael Jonathan

    1998-01-01

    through type I processes (i.e., independent of singlet oxygen), while type II (singlet oxygen) mechanisms may play a significant role in protein carbonyl formation. Reaction of the protein hydroperoxide species with metal ion complexes is shown to produce further protein-derived radicals which...

  10. Iodine-catalyzed addition of 2-mercaptoethanol to chalcone derivatives: Synthesis of the novel β-mercapto carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Gürkan Yerli

    2012-01-01

    Full Text Available In this study, a series of novel β-mercapto carbonyl derivatives (3-(2-hydroxyethylthio-1,3-diarylpropan-1-one (5a-i were prepared by addition of 2-mercaptoethanol (4 to chalcones (3a-i in the presence of catalytic amount of iodine (10 mol % in CH 2Cl 2.

  11. Microwave Promoted Regeneration of Carbonyl Compounds from Oximes Using N, N-Dichloro Poly(Styrene-co-divinylbenzene)Sulphonamide Resin

    OpenAIRE

    A.G. Beldar; Mamta Sharma

    2011-01-01

    An efficient, economically viable and operationally simple method was developed for deoximation of oximes (of ketones and aldehydes) to their corresponding carbonyl compounds using polymer beads of N, N-dichloro poly(styrene-co-divinylbenzene)sulphonamide resin. Polymeric reagent offered speedy conversion and substantial yields of products under mild condition and is recyclable. Deoximation was monitored by the use of 13C NMR.

  12. Pd/C-Catalyzed Carbonylative Esterification of Aryl Halides with Alcohols by Using Oxiranes as CO Sources.

    Science.gov (United States)

    Min, Byul-Hana; Kim, Dong-Su; Park, Hyo-Soon; Jun, Chul-Ho

    2016-04-25

    A carbonylative esterification reaction between aryl bromides and alcohols, promoted by Pd/C and NaF in the presence of oxiranes, has been developed. In this process, oxiranes serve as sources of carbon monoxide by their conversion to aldehydes through a palladium-promoted Meinwald rearrangement pathway. Intramolecular versions of this process serve as methods for the synthesis of lactones and phthalimides.

  13. Double Conjugate Addition of Dithiols to Propargylic Carbonyl Systems To Generate Protected 1,3-Dicarbonyl Compounds

    NARCIS (Netherlands)

    Sneddon, Helen F.; Heuvel, Alexandra van den; Hirsch, Anna K.H.; Booth, Richard A.; Shaw, David M.; Gaunt, Matthew J.; Ley, Steven V.

    2006-01-01

    The work describes the efficient double conjugate addition of ethane and propane dithiols in the presence of sodium methoxide to a wide variety of propargylic carbonyl containing compounds. The products of these reactions are differentiated, 1,3-dicarbonyl systems useful for various synthesis progra

  14. THE MIXTURES OF 2.4-DINITROPHENYLHIDRAZONES OF INFERIOR CARBONYL COMPOUNDS AND THEIR HPLC SEPARATION WITH GRADIENT BINARY MIXTURES PHASES

    Directory of Open Access Journals (Sweden)

    Gheorghe Zgherea

    2008-06-01

    Full Text Available Mixtures of small quantities of carbonyl compounds are presents in foods, concerning sensorial qualities. The inferior carbonyl compounds (C2-C4, boiling point <100°C – mono and dicarbonyl – can be identified and measured their concentrations, after a separation by distillation on the water bath. They are transferred in a strongly acid solution of 2.4-dinitrophenylhidrazine (2.4-DNPH, generating a mixture of insoluble 2.4-dinitrophenylhidrazones (2.4-DNPH-ones. The 2.4-DNPH-ones are organic compounds with weak polarity, solids, crystallized, yellows and water insoluble, soluble in organic solvents. The mixture of 2.4dinitrophenylhidrazones may be separated by liquid chromatography, using the reverse phase mechanism [1-3]. This paper contains experimental and theoretical considerations to the means of separation through liquid chromatography of two synthetically and a natural mixtures that contain 2.4-DNPH-ones provided by inferior carbonyl compounds; to obtain conclude results, in the synthetically mixtures was introduce and 2.4-DNPH-ones provided by carbonyl compounds having three (acetone and propanal and four (isobutyl aldehyde atoms of carbon.

  15. Ligand-Enabled γ-C–H Olefination and Carbonylation: Construction of β-Quaternary Carbon Centers

    OpenAIRE

    Li, Suhua; Chen, Gang; Feng, Chen-Guo; Gong, Wei; Yu, Jin-Quan

    2014-01-01

    Monoselective γ-C–H olefination and carbonylation of aliphatic acids has been accomplished by using a combination of a quinoline-based ligand and a weakly coordinating amide directing group. The reaction provides a new route for constructing richly functionalized all-carbon quaternary carbon centers at the β-position of aliphatic acids.

  16. Ligand-enabled γ-C-H olefination and carbonylation: construction of β-quaternary carbon centers.

    Science.gov (United States)

    Li, Suhua; Chen, Gang; Feng, Chen-Guo; Gong, Wei; Yu, Jin-Quan

    2014-04-09

    Monoselective γ-C-H olefination and carbonylation of aliphatic acids has been accomplished by using a combination of a quinoline-based ligand and a weakly coordinating amide directing group. The reaction provides a new route for constructing richly functionalized all-carbon quaternary carbon centers at the β-position of aliphatic acids.

  17. New Initiation Modes for Directed Carbonylative C–C Bond Activation: Rhodium-Catalyzed (3 + 1 + 2) Cycloadditions of Aminomethylcyclopropanes

    Science.gov (United States)

    2016-01-01

    Under carbonylative conditions, neutral Rh(I)-systems modified with weak donor ligands (AsPh3 or 1,4-oxathiane) undergo N-Cbz, N-benzoyl, or N-Ts directed insertion into the proximal C–C bond of aminomethylcyclopropanes to generate rhodacyclopentanone intermediates. These are trapped by N-tethered alkenes to provide complex perhydroisoindoles. PMID:27709913

  18. Unusual Reaction of β-Hydroxy α-Diazo Carbonyl Compounds with Trichloroacetonitrile (CI3CCN) and Sodium Hydride

    Institute of Scientific and Technical Information of China (English)

    SHI Wei-Feng; JIANG Nan; WANG Jian-Bo

    2003-01-01

    @@ In the process of preparing α-diazo carbonyl compound 2 by imidation of 1, we unexpectedly observed a direct conversion of the hydroxyl group into trichloroacetylamino group. In this presentation, we report this unprecedented reaction, as well as the Rh2(OAc)4-catalyzed reaction of the resulting β-(trichloroacetyl)amino β-diazo carbonylcompounds 3. [ 1

  19. Inhibitory activity of carbonyl compounds on alcoholic fermentation by Saccharomyces cerevisiae.

    Science.gov (United States)

    Cao, Dongxu; Tu, Maobing; Xie, Rui; Li, Jing; Wu, Yonnie; Adhikari, Sushil

    2014-01-29

    Aldehydes and acids play important roles in the fermentation inhibition of biomass hydrolysates. A series of carbonyl compounds (vanillin, syringaldehyde, 4-hydroxybenzaldehyde, pyrogallol aldehyde, and o-phthalaldehyde) were used to examine the quantitative structure-inhibitory activity relationship of carbonyl compounds on alcoholic fermentation, based on the glucose consumption rate and the final ethanol yield. It was observed that pyrogallol aldehyde and o-phthalaldehyde (5.0 mM) reduced the initial glucose consumption rate by 60 and 89%, respectively, and also decreased the final ethanol yield by 60 and 99%, respectively. Correlating the molecular descriptors to inhibition efficiency in yeast fermentation revealed a strong relationship between the energy of the lowest unoccupied molecular orbital (ELUMO) of aldehydes and their inhibitory efficiency in fermentation. On the other hand, vanillin, syringaldehyde, and 4-hydroxybenzaldehyde (5.0 mM) increased the final ethanol yields by 11, 4, and 1%, respectively. Addition of vanillin appeared to favor ethanol formation over glycerol formation and decreased the glycerol yield in yeast fermentation. Furthermore, alcohol dehydrogenase (ADH) activity dropped significantly from 3.85 to 2.72, 1.83, 0.46, and 0.11 U/mg at 6 h of fermentation at vanillin concentrations of 0, 2.5, 5.0, 10.0, and 25.0 mM correspondingly. In addition, fermentation inhibition by acetic acid and benzoic acid was pH-dependent. Addition of acetate, benzoate, and potassium chloride increased the glucose consumption rate, likely because the salts enhanced membrane permeability, thus increasing glucose consumption.

  20. Role of carbonyls and aromatics in the formation of tropospheric ozone in Rio de Janeiro, Brazil.

    Science.gov (United States)

    da Silva, Débora Bonfim Neves; Martins, Eduardo Monteiro; Corrêa, Sergio Machado

    2016-05-01

    The ozone in Rio de Janeiro has been in violation of national air quality standards. Among all of the monitoring stations, the Bangu neighbourhood has the most violations of the national standard of 160 μg m(-3) for the years 2012 and 2013. This study evaluated the reactivity of the carbonyls and aromatics in the tropospheric ozone formation processes. The samples were collected between July and October of 2013. Carbonyls were sampled using SiO2 cartridges coated with C18 and impregnated with 2,4-dinitrophenylhydrazine and were analysed by HPLC. Activated carbon cartridges and GC/MS were used to measure the concentration of monoaromatic hydrocarbons. An air quality monitoring station provided the concentrations of the criteria pollutants and the meteorological parameters. Cluster analysis and a Pearson correlation matrix were used to determine the formation of groups and the correlation of the variables. The evaluation of the volatile organic compounds (VOC) reaction with OH radicals and the MIR scale was used to extrapolate the reactivity of VOCs to the ozone formation. The average concentrations obtained were 19.7 and 51.9 μg m(-3) for formaldehyde and acetaldehyde, respectively. The mean concentrations obtained for aromatics were 1.5, 6.7, 1.5, 2.6 and 1.6 μg m(-3) for benzene, toluene, ethyl benzene, m+p-xylene and o-xylene, respectively. The cluster analysis indicated the presence of three similar groups, with one formed by gaseous criteria pollutants, another formed by the meteorological parameters, ozone and fine particles, and the last group formed by the aromatics. For the two reactivity scales evaluated, acetaldehyde and toluene were the main ozone precursors.

  1. Quantum Chemical Studies of the Substituent Effect on the Reaction of Carbonyl Oxime with Amine.

    Science.gov (United States)

    Kaya, Yunus

    2016-07-21

    The reaction of the two different substitue carbonyl oximes (isonitrosoacetylnaphthaline, inanH and nitro-isonitrosoacetophenone, ninapH) with two different amines (1-phenylethanol amine, pea, and ethanol amine, ea) was carried out and characterized by elemental analyses, IR, and (1)H and (13)C NMR spectroscopic methods. As a result of these experimental studies, two different levels for all reactions were determined: (I) formation of imine oxime and (II) rearrangement of imine oxime or formation of amido alcohol. After a mechanism was suggested for all of these reactions, the reaction mechanism of carbonyl oxime with amine was first studied by means of the B3LYP/6-311G(d,p) method. Because of the deficiency of density functional theory (DFT) on dispersion effects, the wB97X-D/6-311G(d,p) method, which includes dispersion correction, was used to obtain the reaction heat and free energy barriers to explain why the formation (imine oxime) and unexpected rearrangement products (amido alcohol) occurred or did not occur. The statistical thermodynamic method was used to obtain the changes in thermodynamic properties of the studied molecules between 100 and 500 K. From a kinetic viewpoint, the slowest step of the reactions is the IN1-TS2-IN2 step, which determines the steps of the reaction kinetics. In addition, spectroscopic properties such as vibrational and NMR chemical shifts were studied for all of the molecules. The frontier molecular orbitals (FMOs), highest occupied molecular orbitals (HOMOs), and lowest unoccupied molecular orbitals (LUMOs) were monitored for all of the molecules.

  2. The serum protein carbonyl content level in relation to exercise stress test

    Directory of Open Access Journals (Sweden)

    Titiporn Mekrungruangwong

    2012-01-01

    Full Text Available Background: Protein carbonyl (P is oxidatively-modified protein with diagnostic potential for acute myocardial infarction. However, many findings indicated the elevation of serum PC content level related to exercise, which could cause false positive results and limiting the specificity for acute coronary syndrome diagnosis. This study aims to evaluate the level of serum protein carbonyl content in healthy volunteers subjected to exercise stress test (EST. Materials and Methods: Serum from healthy volunteers was collected 5-10 min before performing EST and 1 hour after the EST was achieved. The serum was collected, and the serum PC content level was determined by spectrophotometric DNPH assay. Results: The serum PC content level after exercise stress test was significantly higher than that of before performing EST (0.373 ± 0.05 nM/mg vs. 0.275 ± 0.02 nM/mg, P < 0.0001. The results demonstrated that in both male and female, serum PC content level after EST was significantly higher than that of before performing EST (0.29 ± 0.03 nM/mg vs. 0.36 ± 0.05 nM/mg P < 0.0001 in male, 0.27 ± 0.02 nM/mg vs. 0.38 ± 0.06 nM/mg P < 0.0001 in female, respectively. Conclusions: This study demonstrated that exercise stress test could result in non-specificity and false positive increasing in serum PC content level in healthy subjects, which may cause misinterpretation when using PC as cardiac marker, especially in patients, who underwent exercise stress test or patients who performing heavy physical activities.

  3. Chemical reactivity and biological activity of chalcones and other α,β-unsaturated carbonyl compounds.

    Science.gov (United States)

    Maydt, Daniela; De Spirt, Silke; Muschelknautz, Christian; Stahl, Wilhelm; Müller, Thomas J J

    2013-08-01

    Abstract 1. Chalcones are structural analogues of benzalacetophenone (BAP). Several derivatives have been identified in plants and anticarcinogenic and anti-inflammatory properties were attributed to the compounds, probably related to their direct antioxidant activity or stimulatory effects on the expression of endogenous defence enzymes like hemeoxygenase-1 (HO-1). HO-1 expression is triggered by the Nrf2-Keap1 signalling pathway, initiated by the addition of chalcones to thiol groups of Keap1 via Michael-type reaction. 2. The present study used a model system estimating the reactivity of different synthetic chalcones and other α,β-unsaturated carbonyl compounds with thiols and compared the chemical reactivity with the biological activity, measured by HO-1 expression in human dermal fibroblasts. 3. Chemical reactivity with the thiol group of N-acetylcysteine was determined with 5,5'-dithiobis-(2-nitrobenzoic acid) and followed chemical principles of structure-reactivity relationship. Most reactive were sulforaphane, dimethylfumarate, chalcone 3 ((2E)-1-phenyl-3-pyrimidin-2-ylprop-2-en-1-one) and chalcone 7 (1,3-diphenylprop-2-yn-1-one). This result demonstrates that α,β-unsaturated carbonyl derivatives react with thiols differently. All compounds were also biologically active; however, expression of HO-1 was not only related to the chemical reactivity but also to the lipophilicity of the molecules which likely affected transmembrane uptake. Most efficient inducers of HO-1 expression were BAP, 4-hydroxynonenal and chalcone 1 (4-[(1E)-3-oxo-3-phenylprop-1-en-1-yl]benzonitrile), chalcone 5 ((2E)-1-phenyl-3-[4-(trifluoromethyl)-phenyl]prop-2-en-1-one) and chalcone 7.

  4. The carbonyl scavenger carnosine ameliorates dyslipidaemia and renal function in Zucker obese rats.

    Science.gov (United States)

    Aldini, Giancarlo; Orioli, Marica; Rossoni, Giuseppe; Savi, Federica; Braidotti, Paola; Vistoli, Giulio; Yeum, Kyung-Jin; Negrisoli, Gianpaolo; Carini, Marina

    2011-06-01

    The metabolic syndrome is a risk factor that increases the risk for development of renal and vascular complications. This study addresses the effects of chronic administration of the endogenous dipeptide carnosine (β-alanyl-L-histidine, L-CAR) and of its enantiomer (β-alanyl-D-histidine, D-CAR) on hyperlipidaemia, hypertension, advanced glycation end products, advanced lipoxidation end products formation and development of nephropathy in the non-diabetic, Zucker obese rat. The Zucker rats received a daily dose of L-CAR or D-CAR (30 mg/kg in drinking water) for 24 weeks. Systolic blood pressure was recorded monthly. At the end of the treatment, plasma levels of triglycerides, total cholesterol, glucose, insulin, creatinine and urinary levels of total protein, albumin and creatinine were measured. Several indices of oxidative/carbonyl stress were also measured in plasma, urine and renal tissue. We found that both L- and D-CAR greatly reduced obese-related diseases in obese Zucker rat, by significantly restraining the development of dyslipidaemia, hypertension and renal injury, as demonstrated by both urinary parameters and electron microscopy examinations of renal tissue. Because the protective effect elicited by L- and D-CAR was almost superimposable, we conclude that the pharmacological action of L-CAR is not due to a pro-histaminic effect (D-CAR is not a precursor of histidine, since it is stable to peptidic hydrolysis), and prompted us to propose that some of the biological effects can be mediated by a direct carbonyl quenching mechanism.

  5. Chitosan Prevents Gentamicin-Induced Nephrotoxicity via a Carbonyl Stress-Dependent Pathway

    Directory of Open Access Journals (Sweden)

    Chu-Kung Chou

    2015-01-01

    Full Text Available Aminoglycosides are widely used to treat infections; however, their applications are limited by nephrotoxicity. With the increase of antibiotic resistance, the use of aminoglycosides is inevitable. Low-molecular-weight chitosan (LMWC has shown renal protective effects in dialysis patients. However, no study has evaluated LMWC for preventing aminoglycoside-induced nephrotoxicity or determined the mechanisms underlying the renal protective effects. In this study, LMWC (165 or 825 mg/kg/day or metformin (100 mg/kg/day was orally administered for 13 days to rats with nephropathy induced by gentamicin (GM, a kind of aminoglycoside (150 mg/kg/day i.p. for 6 days. Both LMCW doses improved renal function. Serum creatinine levels improved in rats treated with 165 and 825 mg/kg/day LMWC (from 2.14 ± 0.74 mg/dL to 1.26 ± 0.46 mg/dL and 0.69 ± 0.12 mg/dL, resp., P < 0.05. Blood urea nitrogen levels were also improved in these rats (from 73.73 ± 21.13 mg/dL to 58.70 ± 22.71 mg/dL and 28.82 ± 3.84 mg/dL, resp., P < 0.05. Additionally, renal tissue morphology improved after LMWC treatment, and accumulation of renal methylglyoxal, a damage factor associated with carbonyl stress, was reversed. These results show that LMWC prevents GM-induced renal toxicity via a carbonyl stress-dependent pathway.

  6. Computational study of the carbonyl-ene reaction of encapsulated formaldehyde in Na-FAU zeolite

    Science.gov (United States)

    Sangthong, Winyoo; Probst, Michael; Limtrakul, Jumras

    2005-06-01

    Density-functional theory (B3LYP/6-31G(d,p)) and the ONIOM (Our-own-N-layer Integrated molecular Orbital+molecular Mechanics) approach utilizing two-layer ONIOM schemes (B3LYP/6-31G(d,p):UFF) have been employed to investigate structures of Na-exchanged zeolite-encapsulated formaldehyde (HCHO@Na-zeolite) and their interactions with propylene. The carbonyl-ene reaction of propylene and formaldehyde was studied on three model systems: (1) formaldehyde in Na-exchanged zeolite: HCHO@Na-zeolite/CH 3CH dbnd6 CH 2; (2) naked Na(I) as catalyst: Na(I)/HCHO/CH 3CH dbnd6 CH 2; (3) a bare model where only the reactants are present: HCHO/CH 3CH dbnd6 CH 2. It is found that inclusion of the extended zeolite framework has an effect on the structure and energetics of the adsorption complexes and leads to a lower energy barrier (25.1 kcal/mol) of the reaction as compared to the bare model system (34.4 kcal/mol). If the naked Na(I) interacts with the HCHO/CH 3CH dbnd6 CH 2 complex the energy barrier of the system is even lower than HCHO@Na-zeolite/CH 3CH dbnd6 CH 2, due to the large electrostatic field generated by the naked Na(I) cation (17.5 kcal/mol). The carbonyl-ene reaction of propylene using HCHO@Na-faujasite takes place in a single concerted reaction step.

  7. Temporal variations of atmospheric carbonyls in urban ambient air and street canyons of a Mountainous city in Southwest China

    Science.gov (United States)

    Pang, Xiaobing; Lee, Xinqing

    2010-06-01

    Carbonyl compounds in urban ambient air and street canyons were measured from December 2008 to August 2009 in a mountainous city in southwest China (Guiyang). The formaldehyde yield from the photo-oxidation of isoprene emitted by vegetation was estimated to be in the range of 0.63-3.62 μg m -3 from May to August, which accounted for 28.8-33.4% of ambient formaldehyde. Based on the calculation of photolysis rates and rates of reaction with the OH radical, it was found that photolysis was the predominant sink for formaldehyde and acetone in both summer and winter. For acetaldehyde, photo-oxidation by OH radicals and photolysis were the major sinks in summer while photo-oxidation by OH radicals was the dominant sink in winter. Wet precipitation was found to be an important removal process for the atmospheric carbonyls. In the urban ambient air, the average concentrations of formaldehyde, acetaldehyde, acetone and all carbonyls were 4.8 ± 2.1, 5.7 ± 3.3, 5.1 ± 2.5, and 25.1 ± 9.2 μg m -3 ( n = 139), respectively. The average concentrations of these species in street canyons were 18.8 ± 6.5, 9.4 ± 3.2, 10.9 ± 2.1, and 64.1 ± 16.3 μg m -3 ( n = 62), respectively. The significantly higher carbonyl levels on weekdays (compared to weekends) highlight the contribution of vehicle emissions to carbonyls in the street canyons.

  8. Carbonyl compound emissions from a heavy-duty diesel engine fueled with diesel fuel and ethanol-diesel blend.

    Science.gov (United States)

    Song, Chonglin; Zhao, Zhuang; Lv, Gang; Song, Jinou; Liu, Lidong; Zhao, Ruifen

    2010-05-01

    This paper presents an investigation of the carbonyl emissions from a direct injection heavy-duty diesel engine fueled with pure diesel fuel (DF) and blended fuel containing 15% by volume of ethanol (E/DF). The tests have been conducted under steady-state operating conditions at 1200, 1800, 2600 rpm and idle speed. The experimental results show that acetaldehyde is the most predominant carbonyl, followed by formaldehyde, acrolein, acetone, propionaldehyde and crotonaldehyde, produced from both fuels. The emission factors of total carbonyls vary in the range 13.8-295.9 mg(kWh)(-1) for DF and 17.8-380.2mg(kWh)(-1) for E/DF, respectively. The introduction of ethanol into diesel fuel results in a decrease in acrolein emissions, while the other carbonyls show general increases: at low engine speed (1200 rpm), 0-55% for formaldehyde, 4-44% for acetaldehyde, 38-224% for acetone, and 5-52% for crotonaldehyde; at medium engine speed (1800 rpm), 106-413% for formaldehyde, 4-143% for acetaldehyde, 74-113% for acetone, 114-1216% for propionaldehyde, and 15-163% for crotonaldehyde; at high engine speed (2600 rpm), 36-431% for formaldehyde, 18-61% for acetaldehyde, 22-241% for acetone, and 6-61% for propionaldehyde. A gradual reduction in the brake specific emissions of each carbonyl compound from both fuels is observed with increase in engine load. Among three levels of engine speed employed, both DF and E/DF emit most CBC emissions at high engine speed. On the whole, the presence of ethanol in diesel fuel leads to an increase in aldehyde emissions.

  9. Protein carbonylation and water-holding capacity of pork subjected to frozen storage: effect of muscle type, premincing, and packaging.

    Science.gov (United States)

    Estévez, Mario; Ventanas, Sonia; Heinonen, Marina; Puolanne, Eero

    2011-05-25

    The present work aimed to study the relationship between protein carbonylation and the loss of water-holding capacity (WHC) occurring during frozen storage of porcine muscles. Pork samples corresponding to two different muscle types, glycolytic M. longissimus dorsi (LD) and oxidative M. psoas major (PM), and subjected to two different premincing, minced (MINCED) and intact pork pieces (INTACT), and packaging, vacuum packaged (VACUUM) and packed in oxygen-permeable bags (OXYGEN), procedures were frozen (-18 °C/12 weeks) and analyzed at sampling times upon thawing (weeks 1, 4, 8, and 12) for the relative amount of specific protein carbonyls, α-aminoadipic and γ-glutamic semialdehydes (AAS and GGS, respectively), and their ability to hold water using two different techniques. The formation of protein carbonyls occurred concomitantly with the loss of WHC, and both phenomena were found to be more intense in LD muscles and in MINCED and OXYGEN pork samples. The loss in WHC was from ca. 10 to 30% in 12 weeks, depending on the method of determination. Plausible mechanisms by which protein carbonylation may decrease the WHC of pork samples are thoroughly discussed in the present paper. Besides the likely impact of protein carbonylation in the water-myofibrillar protein relationships, the implication of AAS and GGS in further reactions including plausible cross-linking would explain the decrease of these semialdehydes by the end of frozen storage and would reinforce their liability in the loss of WHC of porcine muscles. The exact nature of these reactions, however, should be investigated in further studies.

  10. Determination of Carbonyl Group Content in Plasma Proteins as a Useful Marker to Assess Impairment in Antioxidant Defense in Patients with Eales′ Disease

    Directory of Open Access Journals (Sweden)

    Rajesh Mohanraj

    2004-01-01

    Full Text Available Purpose: Formation of protein carbonyl groups is considered an early biomarker for the oxidant/antioxidant barrier impairment in various inflammatory diseases. We evaluated the intensity of free radical reactions in patients with Eales′ disease, an idiopathic inflammatory condition of the retina. Methods: Twenty patients with Eales′ disease in active vasculitis stage, 15 patients with Eales′ disease in healed vasculitis stage and 20 healthy control subjects were recruited for the study. Plasma protein carbonyl groups,plasma glutathione (GSH superoxide dismutase (SOD activity and thiobarbituric acid reactive substances (TBARS were determined in erythrocytes. Results: Plasma protein carbonyl content was elevated by a factor of 3.5 and 1.8 respectively in active and healed vasculitis stages. The increase of carbonyl group content in active and healed stage of patients with Eales′ disease correlated with diminished SOD activity and GSH content. There was also increased accumulation of TBARS in active and healed vasculitis stages of Eales′ disease, and this correlated with diminished SOD activity. Conclusion: Our results showed that protein carbonyl group content increases with severity of Eales′ disease. The increase in carbonyl content correlated with diminished antioxidant status. This confirms an earlier report that free radical mediated tissue damage occurs in Eales′ disease. The determination of protein carbonyl content may be used as a simple biomarker to monitor the efficacy of antioxidant supplementation in controlling retinal vasculitis in patients with Eales′ disease.

  11. Carbonyl sulfide (COS) as a tracer to constrain surface carbon fluxes

    Science.gov (United States)

    Yakir, Dan; Berkelhammer, Max; Miller, John; Montzka, Steve; Chen, Huilin

    2014-05-01

    provide additional constraints on the differential responses of photosynthesis and respiration, such as associated with C3 and C4 vegetation. Developing the use of COS as a powerful tracer of photosynthetic CO2 fluxes at all scales can help improve prediction of future responses of the terrestrial biosphere to changing environmental conditions. Key words Carbonyl sulfide, COS, Carbonic anhydrase, CA, ecosystem respiration, GPP, Biosphere-atmosphere interactions, soil COS uptake. References Asaf D, Rotenberg E, Tatarinov T, Dicken U, Montzka SA & Yakir D (2013) Ecosystem photosynthesis inferred from carbonyl sulfide flux measurements. Nature GeoScience, 6, 186-190; DOI: 10.1038/NGEO1730 Berry J, Wolf A, Campbell E, Baker I, Blake N, Blake D, Denning AS, Kawa SR, Montzka SA, Seibt UY, Stimler K, Yakir D Zhu Z (2013) A coupled model of the global cycles of carbonyl sulfide and CO2: A possible new window on the carbon cycle. J. Geophys. Res.: Biogeochem. 118, doi 10.1002/jgrg.20068, 2013 Stimler K, Berry JA, Montzka S, Yakir D (2011) Association between COS uptake and 18D during gas exchange in C3 and C4 leaves. Plant Physiol. Doi 10.1104/pp.111.176578

  12. Influence of Gas Components on the Formation of Carbonyl Sulfide over Water-Gas Shift Catalyst B303Q

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Water-gas shift reaction catalyst at lower temperature (200-400 ℃) may improve the conversion of carbon monoxide. But carbonyl sulfide was found to be present over the sulfided cobaltmolybdenum/alumina catalyst for water-gas shift reaction. The influences of temperature, space velocity,and gas components on the formation of carbonyl sulfide over sulfided cobalt-molybdenum/alumina catalyst B303Q at 200-400 ℃ were studied in a tubular fixed-bed quartz-glass reactor under simulated water-gas shift conditions. The experimental results showed that the yield of carbonyl sulfide over B303Q catalyst reached a maximum at 220 ℃ with the increase in temperature, sharply decreased with the increase in space velocity and the content of water vapor, increased with the increase in the content of carbon monoxide and carbon dioxide, and its yield increased and then reached a stable value with the increase in the content of hydrogen and hydrogen sulfide. The formation mechanism of carbonyl sulfide over B303Q catalyst at 200-400 ℃ was discussed on the basis of how these factors influence the formation of COS. The yield of carbonyl sulfide over B303Q catalyst at 200-400 ℃ was the combined result of two reactions, that is, COS was first produced by the reaction of carbon monoxide with hydrogen sulfide,and then the as-produced COS was converted to hydrogen sulfide and carbon dioxide by hydrolysis. The mechanism of COS formation is assumed as follows: sulfur atoms in the Co9Ss-MoS2/Al2O3 crystal lattice were easily removed and formed carbonyl sulfide with CO, and then hydrogen sulfide in the water-gas shift gas reacted with the crystal lattice oxygen atoms in CoO-MoO3/Al2O3 to form Co9Ss-MoS2/Al2O3.This mechanism for the formation of COS over water-gas shift catalyst B303Q is in accordance with the Mars-Van Krevelen's redox mechanism over metal sulfide.

  13. Conversion du methanol en ethanol par carbonylation suivie d'hydrogenolyse

    Science.gov (United States)

    Gaucher, Melissa

    Ce projet de maîtrise s'inscrit dans le cadre des nouvelles filières énergétiques renouvelables et s'effectue au sein de la Chaire de recherche industrielle sur l'éthanol cellulosique créée par trois partenaires industriels (Enerkem, CRB et Ethanol Greenfield) et le gouvernement du Québec en collaboration avec l'Université de Sherbrooke. La stratégie d'un des partenaires, Enerkem, est de convertir par gazéification des résidus de biomasse non homogène en Syngas, ce gaz est ensuite converti en méthanol puis en éthanol. L'objectif principal de ce projet est la conversion catalytique de l'acétate en alcool. Un catalyseur commercial, composé de cuivre et de chrome, a permis l'obtention des conversions de plus de 95 % et une sélectivité pour l'éthanol de plus de 50 % avec l'acétate de méthyle, de 99 % avec l'acétate d'éthyle et de 50 % avec l'acétate de butyle. Les conditions optimales trouvées impliquent une température de 215 °C, une pression de 350 psig, une vitesse spatiale de 1800 h -1 H2 STP et un ratio H2 : Acétate de 7. Un catalyseur alternatif, à base de cuivre et de zinc, a aussi été testé. L'objectif secondaire est la carbonylation du méthanol en acétate. Cette étape a été réalisée en phase gazeuse où des rendements très élevés, soit plus de 2000 kg d'acétate de méthyle par kg de métal précieux à l'heure (kg AM/ kg métal précieux/h), ont été obtenus. Les conditions d'opérations testées impliquent une température variant entre 200-240 °C, une pression entre 250-600 psig, des ratios McOH : CO de 1 à 2,5. Mots clés: Carbonylation, Éthanol, Hydrogénolyse, Catalyse hétérogène.

  14. Transition-Metal-Catalyzed C-H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds.

    Science.gov (United States)

    Hummel, Joshua R; Boerth, Jeffrey A; Ellman, Jonathan A

    2016-12-12

    The transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom-substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functional group compatibility and without the production of waste byproducts. Additionally, many transition-metal-catalyzed C-H bond additions to polarized π bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition-metal-catalyzed addition of C-H bonds to carbonyls, imines, and related polarized π bonds.

  15. Catalyst- and solvent-dependent stereodivergence in the intramolecular Et(2)Zn/Pd(0) -promoted carbonyl propargylation: mechanistic implications.

    Science.gov (United States)

    Arrate, Mónica; Durana, Aritz; Lorenzo, Paula; de Lera, Ángel R; Álvarez, Rosana; Aurrecoechea, José M

    2013-10-04

    Carbonyl-tethered propargylic benzoates undergo intramolecular carbonylpropargylation upon treatment with Et2 Zn in the presence of a catalytic amount of Pd(0) with the formation of 2-alkynylcyclopentanol products. A ligand/solvent effect on the cis/trans selectivity (referring to the relative positions of alkynyl and OH groups) of ring-closure has been found. In a non-coordinating solvent (benzene), increasing the electron-donating ability of the phosphine ligand (while decreasing its dissociation ability) leads to an increased tendency towards the trans product. On the other hand, the combination of a coordinating solvent (THF) and PPh3 , an easily dissociated phosphine, results in the exclusive formation of cis products. Experimental and computational results are compatible with a divergent behavior of an allenylethylpalladium intermediate that partitions between competitive carbonyl-addition and transmetalation pathways, each leading to a different diastereoisomer. These results also suggest that the dissociating ability of the phosphine regulates that behavior.

  16. Diurnal and seasonal trends in carbonyl levels in a semi-urban coastal site in the Gulf of Campeche, Mexico

    Science.gov (United States)

    Cerón, R. M.; Cerón, J. G.; Muriel, M.

    Concentrations of formaldehyde, acetaldehyde, acetone, propionaldehyde and butyraldehyde were measured in a semi-urban coastal site in the Gulf of Campeche, Mexico, during the winter, summer and autumn seasons. Measurements were carried out from 10 February 2004 to 16 November 2004. Carbonyl compound levels showed pronounced diurnal and seasonal variations. Maximum concentrations occurred between 13:00 h and 16:00 h, when vehicular traffic and photochemical activity were intense, and during the summer (when there was greater solar radiation). Only acetone during the first campaign (winter) did not correlate with temperature; it showed an inverse diurnal pattern, with higher concentrations during the night, probably due to a local and temporal source. The low concentrations of the main carbonyls found in this study, compared with the values reported for other urban areas, seem to indicate that air quality is still satisfactory in Carmen City.

  17. Effects of low concentration biodiesel blends application on modern passenger cars. Part 2: impact on carbonyl compound emissions.

    Science.gov (United States)

    Fontaras, Georgios; Karavalakis, Georgios; Kousoulidou, Marina; Ntziachristos, Leonidas; Bakeas, Evangelos; Stournas, Stamoulis; Samaras, Zissis

    2010-07-01

    Today in most European member states diesel contains up to 5% vol biodiesel. Since blending is expected to increase to 10% vol, the question arises, how this higher mixing ratio will affect tailpipe emissions particularly those linked to adverse health effects. This paper focuses on the impact of biodiesel on carbonyl compound emissions, attempting also to identify possible relationship between biodiesel feedstock and emissions. The blends were produced from five different feedstocks, commonly used in Europe. Measurements were conducted on a Euro 3 common-rail passenger car over various driving cycles. Results indicate that generally the use of biodiesel at low concentrations has a minor effect on carbonyl compound emissions. However, certain biodiesels resulted in significant increases while others led to decreases. Biodiesels associated with increases were those derived from rapeseed oil (approx. 200%) and palm oil (approx. 180%), with the highest average increases observed at formaldehyde and acroleine/acetone.

  18. Synthesis of 3-[(N-carboalkoxy)ethylamino]-indazole-dione derivatives and their biological activities on human liver carbonyl reductase.

    Science.gov (United States)

    Berhe, Solomon; Slupe, Andrew; Luster, Choice; Charlier, Henry A; Warner, Don L; Zalkow, Leon H; Burgess, Edward M; Enwerem, Nkechi M; Bakare, Oladapo

    2010-01-01

    A series of indazole-dione derivatives were synthesized by the 1,3-dipolar cycloaddition reaction of appropriate substituted benzoquinones or naphthoquinones and N-carboalkoxyamino diazopropane derivatives. These compounds were evaluated for their effects on human carbonyl reductase. Several of the analogs were found to serve as substrates for carbonyl reductase with a wide range of catalytic efficiencies, while four analogs display inhibitory activities with IC(50) values ranging from 3-5 microM. Two of the inhibitors were studied in greater detail and were found to be noncompetitive inhibitors against both NADPH and menadione with K(I) values ranging between 2 and 11 microM. Computational studies suggest that conformation of the compounds may determine whether the indazole-diones bind productively to yield product or nonproductively to inhibit the enzyme.

  19. An important missing source of atmospheric carbonyl sulfide: Domestic coal combustion

    Science.gov (United States)

    Du, Qianqian; Zhang, Chenglong; Mu, Yujing; Cheng, Ye; Zhang, Yuanyuan; Liu, Chengtang; Song, Min; Tian, Di; Liu, Pengfei; Liu, Junfeng; Xue, Chaoyang; Ye, Can

    2016-08-01

    Carbonyl sulfide (COS), carbon monoxide (CO), and sulfur dioxide (SO2) emissions generated from prevailing domestic coal stoves fueled with raw bituminous coal were studied under alternation cycles of flaming and smoldering combustion. The measurements in the laboratory and the farmer's house indicated that COS and CO emissions mainly occurred under the condition of flame extinguishment after coal loading, whereas SO2 emissions were mainly generated through combustion with flame. The COS emission factors for the domestic stoves in the laboratory and the farmer's house were recorded as 0.57 ± 0.10 g COS kg-1 and 1.43 ± 0.32 g COS kg-1, being approximately a factor of 50 and 125 greater than that generated from coal power plants, respectively. Based on the COS emission factors measured in this study, COS emission from only domestic coal combustion in China would be at least 30.5 ± 5.6 Gg S yr-1 which was 1 magnitude greater than the current COS estimation from the total coal combustion in China.

  20. Understanding fog-plant interactions at the ecosystem scale using atmospheric carbonyl sulfide

    Science.gov (United States)

    Campbell, J. E.; Whelan, M.; Stinecipher, J.; Zumkehr, A. L.; Berry, J. A.; Dawson, T. E.; Seibt, U.; Hilton, T. W.; Kulkarni, S.; Commane, R.; Angevine, W. M.; Lu, Y.; Herndon, S. C.; Zahniser, M. S.

    2015-12-01

    Ecosystem metabolism is thought to have powerful feedbacks with the climate system as well as direct impacts on individual taxa that rely on ecosystems for food, water, and shelter. Despite the importance of an ecosystem level understanding, climate change impacts on whole ecosystems remains highly uncertain. In particular, coastal fog-dominated regions are a blind spot for whole ecosystem measurements of the land-air-sea exchange of carbon, water, and energy. To address this critical knowledge gap, our inter-displicary team from the University of California's new Institute for the Study of Ecological Effects of Climate Impacts (ISEECI) has launched a next-generation monitoring program along a gradient of UC Natural Reserve System (NRS) sites. We leverage recent breakthroughs in atmospheric spectroscopy and mechanistic ecosystem models of carbonyl sulfide that provide an unprecedented opportunity to explore the sustainability of coastal systems. Here we present our next-generation monitoring and regional analysis across a North/South transect of UC-NRS sites that has the potential to provide a new window into fog-dominated ecosystems, both currently and under climate change scenarios.

  1. Smart absorbing property of composites with MWCNTs and carbonyl iron as the filler

    Science.gov (United States)

    Xu, Yonggang; Yuan, Liming; Cai, Jun; Zhang, Deyuan

    2013-10-01

    A smart absorbing composite was prepared by mixing silicone rubber, multi-walled carbon nanotubes (MWCNTs) and flaky carbonyl iron particles (CIPs) in a two-roll mixer. The complex permittivity and permeability of composites with variable compression strain was measured by the transmission method and dc electric conductivity was measured by the standard four-point contact method, then the reflection loss (RL) could be calculated to evaluate the microwave absorbing ability. The results showed that the applied compression strain made the complex permittivity decrease but not obviously due to the broken original conductive network. The enforcement of the strain on the complex permeability was attributed to the orientation of flaky CIPs. With the compressing strain applied on the composites with thickness 1 mm or 1.5 mm, the RL value decreased (minimum -13.2 dB and -25.1 dB) and the absorbing band (RLsmart absorbing property was effective on preparing absorbers with wide absorption band and high absorption ratio.

  2. Observations of the uptake of carbonyl sulfide (COS by trees under elevated atmospheric carbon dioxide concentrations

    Directory of Open Access Journals (Sweden)

    L. Sandoval-Soto

    2012-02-01

    Full Text Available Global change affects ecosystems to adapt to elevated atmospheric concentrations of carbon dioxide (CO2. We understand that carbonyl sulfide (COS, a trace gas which is involved in building up the stratospheric sulfate aerosol layer, is taken up by vegetation with the same triad of the enzmyes which are metabolizing the CO2, i.e. Ribulose-1,5-bisphosphate Carboxylase-Oxygenase (Rubisco, Phosphoenolpyruvate Carboxylase (PEP-Co and carbonic anhydrase (CA. Therefore, we discuss a physiological/biochemical adaptation of these enzymes to affect the sink strength of vegetation for COS. We investigated the adaption of two European tree species, Fagus sylvatica and Quercus ilex, grown inside chambers under elevated CO2 and determined the exchange characteristics and the content of CA after a 1–2 yr period of adaption from 350 ppm to 800 ppm CO2. We could demonstrate that the COS compensation point, the CA activity and the deposition velocities may change and cause a decrease of the COS uptake by plant ecosystems. As a consequence, the atmospheric COS level may rise leading to higher input of this trace gas into the stratosphere and causing a higher energy reflection by the stratospheric sulfur aerosol into space, thus counteracting the direct radiative forcing by the tropospheric COS.

  3. Comparison of extraction techniques and mass spectrometric ionization modes in the analysis of wine volatile carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Zapata, Julian; Mateo-Vivaracho, Laura; Cacho, Juan [Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragon, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza (Spain); Ferreira, Vicente, E-mail: vferre@unizar.es [Laboratory for Flavor Analysis and Enology, Institute of Engineering of Aragon, I3A, Department of Analytical Chemistry, Faculty of Sciences, University of Zaragoza, 50009 Zaragoza (Spain)

    2010-02-15

    This work presents a comparative study of the analytical characteristics of two methods for the analysis of carbonyl compounds in wine, both based on the derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA). In the first method derivatives are formed in the solid phase extraction (SPE) cartridge in which the analytes have been previously isolated, while in the second method derivatives are formed in a solid phase microextraction (SPME) fibre saturated with vapors of the reagent and exposed to the sample headspace. In both cases detection has been carried out by electron impact (EI) or negative chemical ionization (NCI) mass spectrometry. The possibility of determining haloanisols simultaneously has been also considered. The method based on SPE presents, in general, better analytical properties than the SPME one. Although linearity was satisfactory for both methods (R{sup 2} > 0.99), repeatability of the SPE method (RSD < 10%) was better than that obtained with SPME (9% < RSD < 20%). Detection limits obtained with EI are better for the SPE method except for trihaloanisols, while with NCI detection limits for both strategies are comparable, although the SPME strategy presents worse results for ketones and methional. Detection limits are always lower with NCI, being the improvement most notable for SPME. Recovery experiments show that in the case of SPE, uncertainties are lower than 12% in all cases, while with the SPME method the imprecision plus the existence of matrix effects make the global uncertainty to be higher than 15%.

  4. Carbonyl iron powder surface modification of magnetorheological elastomers for vibration absorbing application

    Science.gov (United States)

    Chen, Dong; Yu, Miao; Zhu, Mi; Qi, Song; Fu, Jie

    2016-11-01

    With excellent characteristic of magnetic-control stiffness, magnetorheological elastomer (MRE) is well suited as a spring element of vibration absorber. To improve the vibration attenuation performance of MRE vibration absorbers, this paper expects to improve the mechanical strength and reduce the loss factor of MRE by interface modification. The surface of carbonyl iron powder (CIP) was modified with silica coating by a simple and convenient approach. Several MRE samples, with different proportions of modified CIPs were fabricated under a constant magnetic field. The morphology and composition of modified CIP were characterized by scanning electron microscope and Fourier transform infrared spectra. The results indicated that the modified CIPs were coated with uniform and continuous silica, which can make a better combination between particle and matrix. The tensile strength, magnetorheological properties and the damping properties of the MRE samples were tested by material testing machine and rheometer. The experimental results demonstrated that the loss factor of the MRE which incorporated with modified CIPs decreased markedly, and the tensile strength of such material has been much improved, at the same time this kind of MRE kept high MR effect. It is expected that this MRE material will meet the requirements of vibration absorber.

  5. Ruthenium(II) carbonyl complexes containing chalconates and triphenylphosphine/arsine

    Indian Academy of Sciences (India)

    P Viswanathamurthi; M Muthukumar

    2011-09-01

    A series of new hexa-coordinated ruthenium(II) carbonyl complexes of the type [RuCl(CO)(EPh3)(B)(L1−4)] (4-15) (E = P or As; B = PPh3, AsPh3 or Py; L = 2'-hydroxychalcone) were synthesized from the reaction of [RuHCl(CO)(EPh3)2(B)] (1-3) (E = P or As; B = PPh3, AsPh3 or Py) with equimolar chalcone in benzene under reflux. The new complexes have been characterized by analytical and spectroscopic (IR, electronic, 1H, 31P{1H}, and 13C NMR) methods. On the basis of data obtained, an octahedral structure has been assigned for all the complexes. The complexes exhibit catalytic activity for the oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of -methylmorpholine--oxide (NMO) as co-oxidant and were also found to be efficient transfer hydrogenation catalysts. The antifungal properties of the ligands and their complexes have also been examined and compared with standard Bavistin.

  6. Structural transitions in electron beam deposited Co–carbonyl suspended nanowires at high electrical current densities

    Directory of Open Access Journals (Sweden)

    Gian Carlo Gazzadi

    2015-06-01

    Full Text Available Suspended nanowires (SNWs have been deposited from Co–carbonyl precursor (Co2(CO8 by focused electron beam induced deposition (FEBID. The SNWs dimensions are about 30–50 nm in diameter and 600–850 nm in length. The as-deposited material has a nanogranular structure of mixed face-centered cubic (FCC and hexagonal close-packed (HCP Co phases, and a composition of 80 atom % Co, 15 atom % O and 5 atom % C, as revealed by transmission electron microscopy (TEM analysis and by energy-dispersive X-ray (EDX spectroscopy, respectively. Current (I–voltage (V measurements with current densities up to 107 A/cm2 determine different structural transitions in the SNWs, depending on the I–V history. A single measurement with a sudden current burst leads to a polycrystalline FCC Co structure extended over the whole wire. Repeated measurements at increasing currents produce wires with a split structure: one half is polycrystalline FCC Co and the other half is graphitized C. The breakdown current density is found at 2.1 × 107 A/cm2. The role played by resistive heating and electromigration in these transitions is discussed.

  7. Structural transitions in electron beam deposited Co-carbonyl suspended nanowires at high electrical current densities.

    Science.gov (United States)

    Gazzadi, Gian Carlo; Frabboni, Stefano

    2015-01-01

    Suspended nanowires (SNWs) have been deposited from Co-carbonyl precursor (Co2(CO)8) by focused electron beam induced deposition (FEBID). The SNWs dimensions are about 30-50 nm in diameter and 600-850 nm in length. The as-deposited material has a nanogranular structure of mixed face-centered cubic (FCC) and hexagonal close-packed (HCP) Co phases, and a composition of 80 atom % Co, 15 atom % O and 5 atom % C, as revealed by transmission electron microscopy (TEM) analysis and by energy-dispersive X-ray (EDX) spectroscopy, respectively. Current (I)-voltage (V) measurements with current densities up to 10(7) A/cm(2) determine different structural transitions in the SNWs, depending on the I-V history. A single measurement with a sudden current burst leads to a polycrystalline FCC Co structure extended over the whole wire. Repeated measurements at increasing currents produce wires with a split structure: one half is polycrystalline FCC Co and the other half is graphitized C. The breakdown current density is found at 2.1 × 10(7) A/cm(2). The role played by resistive heating and electromigration in these transitions is discussed.

  8. Atmospheric measurements of carbonyl sulfide, dimethyl sulfide, and carbon disulfide using the electron capture sulfur detector

    Science.gov (United States)

    Johnson, James E.; Bates, Timothy S.

    1993-01-01

    Measurements of atmospheric dimethyl sulfide (DMS), carbonyl sulfide (COS), and carbon disulfide (CS2) were conducted over the Atlantic Ocean on board the NASA Electra aircraft during the Chemical Instrumentation Test and Evaluation (CITE 3) project using the electron capture sulfur detector (ECD-S). The system employed cryogenic preconcentration of air samples, gas chromatographic separation, catalytic fluorination, and electron capture detection. Samples collected for DMS analysis were scrubbed of oxidants with NaOH impregnated glass fiber filters to preconcentration. The detection limits (DL) of the system for COS, DMS, and CS2 were 5, 5, and 2 ppt, respectively. COS concentrations ranged from 404 to 603 ppt with a mean of 489 ppt for measurements over the North Atlantic Ocean (31 deg N to 41 deg N), and from 395 to 437 ppt with a mean of 419 ppt for measurements over the Tropical Atlantic Ocean (11 deg S to 2 deg N). DMS concentrations in the lower marine boundary layer, below 600-m altitude, ranged from below DL to 150 ppt from flights over the North Atlantic, and from 9 to 104 ppt over the Tropical Atlantic. CS2 concentrations ranged from below DL to 29 ppt over the North Atlantic. Almost all CS2 measurements over the Tropical Atlantic were below DL.

  9. Infrared multiphoton dissociation of unsubstituted metal carbonyls at 5 μm

    Science.gov (United States)

    Au, Mei-Kuen; Hackett, P. A.; Humphries, M.; John, P.

    1984-01-01

    A frequency-doubled carbon dioxide laser of modest output energy (1 mJ) has been used to study, for the first time, the infrared multiphoton absorption by, and dissociation of, the unsubstituted carbonyls of vanadium, chromium, iron, nickel, molybdenum, and tungsten. The multiphoton absorption cross-sections measured for Ni(CO)4, Fe(CO)5, Cr(CO)6, Mo(CO)6, and V(CO)6 are high (σ˜2×10-17) and ensure facile multiphoton dissociation. In focussed beams a pressure independent reaction yield proportional to the 1.5 power of the beam energy is observed for Fe(CO)5, Cr(CO)6, and Mo(CO)6 implying threshold fluences of only 32, 25, and 26 mJ cm-2, respectively. The stoichiometry of the reaction, observed by a pressure measurement technique, is consistent with production of metal atoms and carbon monoxide as final products for Ni(CO)4, Fe(CO)5, Cr(CO)6, and Mo(CO)6. This extensive decarbonylation along the ground state surface is consistent with recent studies of the photochemistry of these molecules from excited electronic states.

  10. The Potential of Carbonyl Sulfide as a Tracer for Gross Primary Productivity at Flux Tower Sites

    Science.gov (United States)

    Blonquist, J.; Montzka, S. A.; Yakir, D.; Desai, A. R.; Dragoni, D.; Griffis, T. J.; Monson, R. K.; Munger, J. W.; Scott, R. L.; Bowling, D. R.

    2010-12-01

    Regional/continental scale studies of atmospheric carbonyl sulfide (OCS) seasonal dynamics and leaf level studies of plant OCS uptake have shown a close relationship to CO2 dynamics and uptake, suggesting potential for OCS as a tracer for gross primary productivity (GPP). Canopy CO2 and OCS differences (mole fraction within canopy minus that above canopy) at a temperate deciduous forest (Harvard Forest AmeriFlux site) were analyzed relative to net ecosystem exchange (NEE) and GPP, respectively. Canopy CO2 and OCS vertical gradients (CO2 and OCS differences divided by within and above canopy measurement height differences) were used to calculate ecosystem relative uptake (ERU; relative canopy OCS gradient divided by relative canopy CO2 gradient, where relative gradients are gradients normalized by above canopy mole fractions), from which GPP was estimated using an equation that assumes OCS follows the same physical pathway as CO2 into plant leaves and where GPP / NEE was proportional to OCS gradient / CO2 gradient. Additionally, canopy CO2 differences from five other AmeriFlux sites were analyzed, and OCS differences were projected from these differences (via an assumed ERU) to further evaluate OCS as a potential GPP tracer. At Harvard Forest, canopy CO2 differences were related to NEE (y = 0.041x + 0.046, r2 = 0.14, P ERU is potentially measurable with current grab-sample-based OCS measurement capabilities and may provide an alternative means of estimating GPP at flux tower sites.

  11. [Purification and characterization of carbonyl enantioselective reductase from Morganella morganii J-8].

    Science.gov (United States)

    Zhang, Peng-Hu; Zhang, Liang; Lu, Yan; Shi, Gui-Yang

    2007-03-01

    The purification and the characteristics of an enzyme from Morganella morganii J-8, which could produce d-pseudoephedrine from 1-phenyl-2-methylamine-acetone, were performed in this study. In this research, first, cells were disrupted by ultrasonic treatment at 4 degrees C. The carbonyl enantioselective reductase was purified with a combination of ammonium precipitation, Phenyl Superose hydrophobic chromatography, DEAE anion exchange, and native polyacrylamide gel electrophoresis. The molecular mass of the purified enzyme subunit was estimated to be 42.5kD on sodium dodecyl sulfate-polyacrylamide electrophoresis (SDS-PAGE). The native molecular mass of the enzyme that was analyzed by high-performance liquid chromatography was found out to be 84.1 kD, which indicated that the enzyme was a dimmer. The purified enzyme was analyzed by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and the result showed that the purified enzyme had high homology with leucine dehydrogenase.

  12. White light generation by carbonyl based indole derivatives due to proton transfer: an efficient fluorescence sensor.

    Science.gov (United States)

    Singla, Nidhi; Bhadram, Venkata Srinu; Narayana, Chandrabhas; Chowdhury, Papia

    2013-04-01

    The motivation of the present work is to understand the optical, chemical, and electrical aspects of the proton transfer mechanism of indole (I) and some carbonyl based indole derivatives: indole-3-carboxaldehyde (I3C) and indole-7-carboxaldehyde (I7C) for both powder form and their liquid solution. Structural information for indole derivatives (isolated molecule and in solution) is obtained with density functional theory (DFT) and time dependent DFT (TD-DFT) methods. Calculated transition energies are used to generate UV-vis, FTIR, Raman, and NMR spectra which are later verified with the experimental spectra. The occurrence of different conformers [cis (N(c)), trans (N(t)), and zwitterion (Z*)] have been interpreted by Mulliken charge, natural bond orbital (NBO) analysis, and polarization versus electric field (P-E loop) studies. (1)H and (13)C NMR and molecular vibrational frequencies of the fundamental modes established the stability of Nc due to the presence of intramolecular hydrogen bonding (IHB) in the ground state (S0). Computed/experimental UV-vis absorption/emission studies reveal the creation of new species: zwitterion (Z*) and anion (A*) in the excited state (S1) due to excited state intramolecular and intermolecular proton transfer (ESI(ra)PT and ESI(er)PT). Increased electrical conductivity (σ(ac)) with temperature and increased ferroelectric polarization at higher field verifies proton conduction in I7C.

  13. Ferricytochrome (c) directly oxidizes aminoacetone to methylglyoxal, a catabolite accumulated in carbonyl stress.

    Science.gov (United States)

    Sartori, Adriano; Mano, Camila M; Mantovani, Mariana C; Dyszy, Fábio H; Massari, Júlio; Tokikawa, Rita; Nascimento, Otaciro R; Nantes, Iseli L; Bechara, Etelvino J H

    2013-01-01

    Age-related diseases are associated with increased production of reactive oxygen and carbonyl species such as methylglyoxal. Aminoacetone, a putative threonine catabolite, is reportedly known to undergo metal-catalyzed oxidation to methylglyoxal, NH4(+) ion, and H2O2 coupled with (i) permeabilization of rat liver mitochondria, and (ii) apoptosis of insulin-producing cells. Oxidation of aminoacetone to methylglyoxal is now shown to be accelerated by ferricytochrome c, a reaction initiated by one-electron reduction of ferricytochrome c by aminoacetone without amino acid modifications. The participation of O2(•-) and HO (•) radical intermediates is demonstrated by the inhibitory effect of added superoxide dismutase and Electron Paramagnetic Resonance spin-trapping experiments with 5,5'-dimethyl-1-pyrroline-N-oxide. We hypothesize that two consecutive one-electron transfers from aminoacetone (E0 values = -0.51 and -1.0 V) to ferricytochrome c (E0 = 0.26 V) may lead to aminoacetone enoyl radical and, subsequently, imine aminoacetone, whose hydrolysis yields methylglyoxal and NH4(+) ion. In the presence of oxygen, aminoacetone enoyl and O2(•-) radicals propagate aminoacetone oxidation to methylglyoxal and H2O2. These data endorse the hypothesis that aminoacetone, putatively accumulated in diabetes, may directly reduce ferricyt c yielding methylglyoxal and free radicals, thereby triggering redox imbalance and adverse mitochondrial responses.

  14. The Behaviour of Protein Carbonyls in Newborns with Birth Respiratory Distress and Asphyxia

    Directory of Open Access Journals (Sweden)

    Gabriela ZAHARIE

    2009-12-01

    Full Text Available Objective: A prospective study was carried out in premature newborns with respiratory distress syndrome (RDS and asphyxia at birth in order to identify and analyze the effects of RDS on proteins. Material and Methods: Protein peroxidation was studied using the Reznick spectrophotometric method. The study group included 14 premature newborns with respiratory distress and asphyxia at birth. The control group included 13 newborns that were born on term, eutrophic and healthy. The determinations were carried out using venous blood. Statistical data analyses were performed using Statistica software. The comparisons between groups (study and controls were performed by applying parametric and non-parametric tests according with the type of distribution. Results: Statistically significant correlations were found between the value of protein carbonyls (PC and the weight of premature newborns in the case group (p < 0.05, as well as between the PC value and the presence of respiratory distress due to surfactant deficiency in the study group. The average PC value in the study group was higher in the third day as compared with the first day. The PC value was significantly higher in the control group as compared with study group. Conclusion: The results of our study revealed that the respiratory distress in the premature newborn and oxygen therapy stimulate the peroxidation of proteins.

  15. Triterpene hexahydroxydiphenoyl esters and a quinic acid purpurogallin carbonyl ester from the leaves of Castanopsis fissa.

    Science.gov (United States)

    Huang, Yong-Lin; Tsujita, Takaaki; Tanaka, Takashi; Matsuo, Yosuke; Kouno, Isao; Li, Dian-Peng; Nonaka, Gen-ichiro

    2011-11-01

    Triterpene hexahydroxydiphenoyl (HHDP) esters have only been isolated from Castanopsis species, and the distribution of these esters in nature is of chemotaxonomical interest. In this study, the chemical constituents of the leaves of Castanopsis fissa were examined in detail to identify and isolate potential HHDP esters. Together with 53 known compounds, 3,4-di-O-galloyl-1-O-purpurogallin carbonyl quinic acid (1) and 3,24-(S)-HHDP-2α,3β,23,24-tetrahydroxytaraxastan-28,20β-olide (2) were isolated and their structures were elucidated by spectroscopic and chemical methods. The polyphenols of the leaves were mainly composed of galloyl quinic acids, triterpenes HHDP esters, ellagitannins and flavonol glycosides. In particular, the isolation yields of 1,3,4-trigalloyl quinic acid and compound 2 were 1.53% and 0.27%, respectively, from the fresh leaves. The presence of lipid soluble HHDP esters of oleanane-type triterpenes as one of the major metabolites is an important chemotaxonomical discovery. Lipase inhibition activities and ORAC values of the major constituents were compared. The triterpene HHDP ester showed moderate lipase inhibition activity and myricitrin gave the largest ORAC value.

  16. Emissions of polyciclic aromatic hydrocarbons and polyciclic carbonyl biphenils from electric arc furnaces

    Directory of Open Access Journals (Sweden)

    P. Gomes, J. F.

    2008-06-01

    Full Text Available This paper describes work done in order to determine the emissions of highly toxic organic micropollutants from electric arc furnaces used in the production of carbon steel from scrap. The study will be allowing to derive relationships between the levels of airborne micropollutants and the operational parameters of the production process so that an abatement of pollution could be achieved. By using the European standard method CEN 1948 for dioxin like compounds sampling and measurement, it was possible to determine the characteristic fingerprint of micropollutants such as polyciclic aromatic hydrocarbons (PAHs and polycyclic carbonyl biphenils (PCBs emitted by this particular stationary source.

    Este artículo contiene resultados del trabajo ejecutado para estudiar la determinación de las emisiones de los micropolutantes orgánicos muy tóxicos que se emiten por los hornos eléctricos de arco utilizados en la producción de acero. Este estudio inicial va a permitir relacionar las concentraciones de polutantes emitidos a la atmósfera con las condiciones de operación del horno eléctrico de arco. Utilizando el método normalizado CEN 1948 para captación y análisis de muestras de compuestos análogos a las dioxinas ha sido posible determinar el perfil característico de los micropolutantes tales como PAHs y PCBs emitidos por esta fuente.

  17. Protein carbonyl levels correlate with performance in elite field hockey players.

    Science.gov (United States)

    Rosa-Lima, Frederico Luis; Lannes, Luiz; Viana-Gomes, Diego; Pierucci, Anna Paola T R; Salerno, Verônica P

    2015-07-01

    Excess and incorrectly selected exercise can degrade athletic performance from an imbalance in redox homeostasis and oxidative stress, but well-planned training and nutrition can improve antioxidant capacity. The aim of the study was to investigate how nutrient intake could influence oxidative stress and cell lesion biomarkers after 5 days of training followed by a game. Blood was collected from 10 athletes at the start of training (basal), after training (pre-game), and postgame. Their acceleration capacity also was measured pre- and postgame. Blood analysis showed an increase in lactate concentration postgame (13%) and total antioxidant capacity increased both pre-game (13.1%) and postgame (12.7%), all in comparison with basal levels. An oxidative stress marker, protein carbonyl (PC), increased 3-fold over the course of the game, which correlated with a decreased acceleration (r = 0.749). For biomarkers of tissue damage, creatine kinase and aspartate transaminase (AST) increased postgame by 150% and 75%, respectively. The AST variation had a high negative correlation with energy and carbohydrate consumption and a moderate correlation with lipid and vitamin C intake. Protein intake had a positive but moderate correlation with reduced glutathione. The observed correlations suggest that nutritional monitoring can improve exercise physiological homeostasis and that PC serves as a good biomarker for oxidative stress and performance loss.

  18. Enhanced microwave absorbing properties of carbonyl iron-doped Ag/ordered mesoporous carbon nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Wu Hongjing, E-mail: wuhongjing@mail.nwpu.edu.cn [Department of Applied Physics, School of Science, Northwestern Polytechnical University, Xi' an 710072 (China); Wang Liuding, E-mail: wangld@nwpu.edu.cn [Department of Applied Physics, School of Science, Northwestern Polytechnical University, Xi' an 710072 (China); Wang Yiming; Guo Shaoli; Shen Zhongyuan [Department of Applied Physics, School of Science, Northwestern Polytechnical University, Xi' an 710072 (China)

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer Ag/OMC-CI paraffin wax composites were successfully prepared. Black-Right-Pointing-Pointer Reflection loss value below -10 dB at 12 GHz was obtained. Black-Right-Pointing-Pointer Ag/OMC-CI showed excellent microwave absorption with respect to OMC-CI and Ag/OMC. Black-Right-Pointing-Pointer This could be attributed to the enhancement of interfacial polarization. - Abstract: Microwave absorbing materials carbonyl iron (CI)-doped Ag/ordered mesoporous carbon (OMC) paraffin wax composites were prepared by colloidal deposition and impregnation methods, and their electromagnetic and microwave absorbing properties were investigated in the frequency ranging from 2 to 18 GHz. The microstructures and chemical compositions of the Ag/OMC and Ag/OMC-CI paraffin wax composites were characterized by TEM, XRD, XPS, SEM and EDS, respectively. The complex permittivity of the paraffin wax composites show dual resonance behavior, resulting from the multi-interfaces among Ag nanoparticles, OMC nanorods, CI and paraffin wax. The magnetic loss was mainly caused by natural resonance and eddy current loss, respectively. The minimum reflection loss (RL) value of Ag/OMC-CI was below -10 dB at 12 GHz, which were superior to those of OMC-CI and Ag/OMC. This phenomenon is attributed to the enhancement of dielectric polarization and magnetic loss.

  19. Review of the toxicology of carbonyl sulfide, a new grain fumigant.

    Science.gov (United States)

    Bartholomaeus, Andrew R; Haritos, Victoria S

    2005-12-01

    Carbonyl sulfide (COS) is a new grain fumigant which has been developed to replace methyl bromide, being phased out due to its ozone depletion properties, and to supplement phosphine gas which is experiencing increased insect resistance. Treatment of commodities with COS, a highly effective fumigant, results in residues that are near or indistinguishable to natural background levels of this compound. COS is a naturally occurring gas, being the predominant sulfur moiety in the atmosphere, occurs naturally in food and is a normal by-product of mammalian aerobic metabolism. COS has low acute inhalational toxicity but with a steep dose response curve; COS is neither genotoxic nor a developmental toxicant but does reversibly impair male fertility. Prolonged, repeated exposure to COS is likely to present similar neurotoxicity hazards to that of the structurally and toxicologically related compound carbon disulfide. Although the occupational risks presented by COS as a fumigant of bulk grain are significant, these are, as they have been for a considerable time for phosphine and methyl bromide, manageable by good occupational safety practices. Consideration may need to be given to scrubbing of ventilated COS and its breakdown product hydrogen sulfide, at the completion of fumigation to minimise worker and bystander exposure. In terms of classical regulatory toxicology studies, the available database for COS is deficient in many aspects and registration in most jurisdictions will depend on sound scientific argument built upon the totality of the existing scientific data as there are strong arguments supporting the registration of this compound.

  20. A glutathione-based system for defense against carbonyl stress in Haemophilus influenzae

    Directory of Open Access Journals (Sweden)

    Kidd Stephen P

    2012-07-01

    Full Text Available Abstract Background adhC from Haemophilus influenzae encodes a glutathione-dependent alcohol dehydrogenase that has previously been shown to be required for protection against killing by S-nitrosoglutathione (GSNO. This group of enzymes is known in other systems to be able to utilize substrates that form adducts with glutathione, such as aldehydes. Results Here, we show that expression of adhC is maximally induced under conditions of high oxygen tension as well as specifically with glucose as a carbon source. adhC could also be induced in response to formaldehyde but not GSNO. An adhC mutant was more susceptible than wild-type Haemophilus influenzae Rd KW20 to killing by various short chain aliphatic aldehydes, all of which can be generated endogenously during cell metabolism but are also produced by the host as part of the innate immune response. Conclusions These results indicate that AdhC plays a role in defense against endogenously generated reactive carbonyl electrophiles in Haemophilus influenzae and may also play a role in defense against the host innate immune system.

  1. Exchange of carbonyl sulfide (COS between the atmosphere and various soils in China

    Directory of Open Access Journals (Sweden)

    J. Liu

    2009-11-01

    Full Text Available Using a dynamic enclosure, the exchange fluxes of carbonyl sulfide (COS between the atmosphere and 18 soils from 10 provinces in China were investigated. The emission or uptake of COS from the soils was highly dependent on the soil type, soil temperature, soil moisture, and atmospheric COS mixing ratio. In general, with the only exception being paddy soils, the soils in this investigation acted as sinks for atmospheric COS under wide ranges of soil temperature and soil moisture. Two intensively investigated wheat soils and one forest soil, had optimal soil temperatures for COS uptake of around 15°C, and the optimal soil water content varied from 13 to 58%. The two paddy soils, exponentially COS emission fluxes increased with increasing soil temperature, and decreased COS emission fluxes with increased soil water content. However, negligible emission was found when the paddy soils were under waterlogging status. The observed compensation points for various soils were different and increased significantly with soil temperature. The laboratory simulation agreed with the preliminary field measurements for the paddy soil in Jiaxing, Zhejiang province.

  2. Carbonyl sulfide and dimethyl sulfide exchange between lawn and the atmosphere

    Science.gov (United States)

    Geng, Chunmei; Mu, Yujing

    2004-06-01

    The exchange of carbonyl sulfide (COS) between lawn and the atmosphere was investigated by using a static enclosure under natural field conditions. The results indicated that the lawn acted as a sink for atmospheric COS and a source of dimethyl sulfide (DMS). The exchange fluxes of COS and DMS ranged between -3.24 pmol m-2 s-1 and -94.52 pmol m-2 s-1, and between 0 and 3.14 pmol m-2 s-1, respectively. The lawn was capable of continuously absorbing COS in nighttime as well as in daytime. The COS fluxes depended strongly on the ambient COS mixing ratios. The dependency of DMS emission fluxes on temperature was observed in November 2002. Soil also acted as a sink for COS during our study. However, the COS exchange fluxes of the lawn were much higher than that of the soil. The average COS and DMS fluxes were much higher in spring than in autumn and in summer. The daytime vertical profiles of COS also indicated that the lawn acted as a net sink for COS.

  3. Forest fluxes of carbonyl sulfide: the balance between photosynthetic and soil uptake

    Science.gov (United States)

    Commane, R.; Herndon, S. C.; McLaren, J.; McManus, J. B.; Meredith, L. K.; Munger, J. W.; Nelson, D. D.; Zahniser, M. S.; Wofsy, S. C.

    2011-12-01

    Recent studies have suggested that carbonyl sulfide (COS) can be used as a proxy for partitioning between photosynthetic uptake and respiratory emission of CO2, a balance which cannot be directly determined through the measurement of CO2 fluxes. COS is the most abundant sulfur containing gas in the atmosphere, with a dominant sink in the terrestrial biosphere. COS is taken up by plants through photosynthesis, but is not respired. It is also lost via uptake to soils. However, in terrestrial ecosystems the magnitudes of soil vs. leaf uptake are not well resolved. We report data from direct, continuous measurements of COS using infrared laser absorption (3 std deviation of less than 10 ppt in 30 s), operated continuously since October, 2010 at Harvard Forest in Western Massachusetts. These data were collected in parallel with long term CO2 and H2 flux measurements. We present seasonal variations of the gradients and fluxes of COS through the forest canopy. Additionally, we investigate the relationship of COS with photosynthesis and soil processes through comparison with CO2 and H2 trace gases, respectively.

  4. Global budget of atmospheric carbonyl sulfide: Temporal and spatial variations of the dominant sources and sinks

    Science.gov (United States)

    Kettle, A. J.; Kuhn, U.; von Hobe, M.; Kesselmeier, J.; Andreae, M. O.

    2002-11-01

    The spatial and temporal variability of the global fluxes of carbonyl sulfide (COS) is discussed together with possible implications for total column atmospheric COS loading. The input of COS into the atmosphere is calculated as the sum of all known direct sources of COS plus the conversion of carbon disulfide (CS2) and dimethyl sulfide (DMS) to COS by atmospheric oxidation processes. Recent models are used to predict COS, CS2, and DMS release from the oceans and COS uptake by soils, plants, and oceans. This forward approach to constructing global integrated COS fluxes has a large associated range of uncertainty. The best guess global annual-integrated COS net flux estimate does not differ from zero within the range of estimated uncertainty, consistent with the observed absence of long-term trends in atmospheric COS loading. Interestingly, the hemispheric time-dependent monthly fluxes are very close in phase for the Northern and Southern Hemispheres. The monthly variation of the Northern Hemisphere flux seems to be driven primarily by high COS vegetation uptake in summer, while the monthly variation of the Southern Hemisphere flux appears to be driven mostly by high oceanic fluxes of COS, CS2, and DMS in summer.

  5. Degradation and emission of carbonyl sulfide, an atmospheric trace gas, by fungi isolated from forest soil.

    Science.gov (United States)

    Masaki, Yoshihito; Ozawa, Rie; Kageyama, Kei; Katayama, Yoko

    2016-09-01

    Soil is thought to be important both as a source and a sink of carbonyl sulfide (COS) in the troposphere, but the mechanism affecting COS uptake, especially for fungi, remains uncertain. Fungal isolates that were collected randomly from forest soil showed COS-degrading ability at high frequencies: 38 out of 43 isolates grown on potato dextrose agar showed degradation of 30 ppmv COS within 24 h. Of these isolates, eight degraded 30 ppmv of COS to below the detection limit within 2 h. These isolates also showed an ability to degrade COS included in ambient air (around 500 pptv) and highly concentrated (12 500 ppmv) level, even though the latter is higher than the lethal level for mammals. COS-degrading activity was estimated by using ergosterol as a biomass index for fungi. Trichoderma sp. THIF08 had the highest COS-degrading activity of all the isolates. Interestingly, Umbelopsis/Mortierella spp. THIF09 and THIF13 were unable to degrade 30 ppmv COS within 24 h, and actually emitted COS during the cultivation in ambient air. These results indicate a fungal contribution to the flux of COS between the terrestrial and atmospheric environments.

  6. Assessing soil fluxes of carbonyl sulfide to aid in ecosystem estimates of GPP

    Science.gov (United States)

    Whelan, M.; Rhew, R. C.; Campbell, J. E.; Hilton, T. W.; Berkelhammer, M. B.; Zumkehr, A. L.; Berry, J. A.

    2014-12-01

    Measuring the draw down of carbonyl sulfide (chemical formula: COS) over ecosystems can provide a new tool for estimating gross primary production (GPP) at important temporal and spatial scales. COS is a gas ubiquitous in the atmosphere that shares many characteristics with CO2: both are taken up by enzymes in plant leaves at a predictable ratio and in proportion to their ambient concentrations. While CO2 is simultaneously respired by soil and plant roots, the dominant flux of COS is foliar absorption. Previously, ecosystem soil fluxes of COS were thought to be negligible in the application of this COS-GPP proxy. Here we present new data describing controls on soil fluxes as a way to anticipate COS soil exchange over heterogeneous landscapes. Using soil samples from two agricultural sites in the Great Plains and one site in the Colorado Desert, we captured data from the extremes of ecosystem GPP in the United States. We then built a model describing COS soil fluxes with inputs of soil temperature and soil water content based on characterized soil behavior. This study provides an essential refinement in applying COS-GPP estimates over the continents.

  7. Exchange of carbonyl sulfide (COS) between the atmosphere and various soils in China

    Science.gov (United States)

    Liu, J.; Geng, C.; Mu, Y.; Zhang, Y.; Xu, Z.; Wu, H.

    2010-02-01

    Using a dynamic enclosure, the exchange rates of carbonyl sulfide (COS) between the atmosphere and 18 soils from 12 provinces in China were investigated. The emission or uptake of COS from the soils was highly dependent on the soil type, soil temperature, soil moisture, and atmospheric COS mixing ratio. In general, with the only exception being paddy soils, the soils in this investigation acted as sinks for atmospheric COS under wide ranges of soil temperature and soil moisture. Two intensively investigated wheat soils and one forest soil had optimal soil temperatures for COS uptake of around 15 °C, and the optimal soil water content varied from 13% to 58%. COS emission rates from the two paddy soils increased exponentially with increment of the soil temperature, and decreased with increasing the soil water content. However, negligible emission was found when the paddy soils were under waterlogging status. The observed compensation points for various soils were different and increased significantly with soil temperature. The laboratory simulation agreed with the preliminary field measurements for the paddy soil in Jiaxing, Zhejiang province.

  8. Exchange of carbonyl sulfide (COS between the atmosphere and various soils in China

    Directory of Open Access Journals (Sweden)

    J. Liu

    2010-02-01

    Full Text Available Using a dynamic enclosure, the exchange rates of carbonyl sulfide (COS between the atmosphere and 18 soils from 12 provinces in China were investigated. The emission or uptake of COS from the soils was highly dependent on the soil type, soil temperature, soil moisture, and atmospheric COS mixing ratio. In general, with the only exception being paddy soils, the soils in this investigation acted as sinks for atmospheric COS under wide ranges of soil temperature and soil moisture. Two intensively investigated wheat soils and one forest soil had optimal soil temperatures for COS uptake of around 15 °C, and the optimal soil water content varied from 13% to 58%. COS emission rates from the two paddy soils increased exponentially with increment of the soil temperature, and decreased with increasing the soil water content. However, negligible emission was found when the paddy soils were under waterlogging status. The observed compensation points for various soils were different and increased significantly with soil temperature. The laboratory simulation agreed with the preliminary field measurements for the paddy soil in Jiaxing, Zhejiang province.

  9. Salt marsh vegetation as a carbonyl sulfide (COS) source to the atmosphere

    Science.gov (United States)

    Whelan, Mary E.; Min, Dong-Ha; Rhew, Robert C.

    2013-07-01

    Carbonyl sulfide (COS) is the most abundant and longest-lived reduced sulfur compound in the atmosphere; changes in its atmospheric concentration could significantly affect global climate and the biogeochemical sulfur cycle. The largest sink of COS in the troposphere is its destruction in plant leaves by the enzymes involved in photosynthesis. In this study, net fluxes of COS were measured from a coastal salt marsh on a subtropical barrier island on the Texas shore of the Gulf of Mexico. We find net emissions from sites with the common salt marsh plant Batis maritima compared to the net uptake from vegetated plots of most previously investigated biomes. The magnitude of the COS production from vegetated plots in this study was twice the emissions of soil-only salt marsh plots. This is the first time that emissions of COS have been found to be significantly enhanced by the presence of vegetation compared to soil alone. COS fluxes exceeded +110 pmol m-2 s-1 for non-inundated plots during daytime hours and were correlated with soil temperature at the depth of 5 cm. Tidal flooding inhibited soil COS exchange; however, we found continued net emissions from emergent B. maritima. This study suggests that emissions of COS resulted from interactions with the plants themselves, which would mean that B. maritima can mediate the production of atmospheric COS.

  10. Controlling variables for the uptake of atmospheric carbonyl sulfide by soil

    Science.gov (United States)

    Kesselmeier, J.; Teusch, N.; Kuhn, U.

    1999-05-01

    Soil samples from arable land were investigated for their exchange of carbonyl sulfide (COS) with the atmosphere under controlled conditions using dynamic cuvettes in a climate chamber. The investigated soil type acted as a significant sink for the trace gas COS. Atmospheric COS mixing ratios, temperature, and soil water content were found to be the physicochemical parameters controlling the uptake. Emission was never observed under conditions representative of a natural environment. The observed compensation point (i.e., an ambient concentration where the consumption and production balance each other and the net flux is zero) for the uptake was about 53 parts per trillion. Uptake rates ranged between 1.5 and 10.3 pmol m-2 s-1. The consumption of COS by the soil sample depended on the physiological activity of the microorganisms in the soil, as indicated by a clear optimum temperature and by a drastic inhibition in the presence of the enzyme inhibitor 6-ethoxy-2-benzothiazole-2-sulfonamide (EZ), a specific inhibitor for carbonic anhydrase.

  11. Carbonyl sulfide exchange on an ecosystem scale: soil represents a dominant sink for atmospheric COS

    Science.gov (United States)

    Kuhn, U.; Ammann, C.; Wolf, A.; Meixner, F. X.; Andreae, M. O.; Kesselmeier, J.

    The soil/plant/atmosphere exchange of carbonyl sulfide (COS) was investigated in an open oak woodland ecosystem at a rural site in northern California. Measurements of atmospheric concentrations of COS were made in June and in December 1994. We found a significant diel cycle with a drop of COS levels by approximately 150 ppt during the night in both seasons. The mean COS daytime background mixing ratios showed a distinct seasonal difference with 465±77 ppt in summer and 375±56 ppt in winter. The nighttime bulk COS flux into the ecosystem was estimated using a micrometeorological model. To address the observed depletion of COS during stable nocturnal boundary layer conditions, the potential of various ecosystem compartments to act as a sink for COS was investigated. Studies using dynamic enclosures flushed with ambient air excluded vegetation as an important sink during nighttime due to high stomatal resistance. Results from soil chamber measurements indicate that the soil can act as a dominant sink for atmospheric COS.

  12. The flux of carbonyl sulfide and carbon disulfide between the atmosphere and a spruce forest

    Directory of Open Access Journals (Sweden)

    X. Xu

    2002-01-01

    Full Text Available Turbulent fluxes of carbonyl sulfide (COS and carbon disulfide (CS2 were measured over a spruce forest in Central Germany using the relaxed eddy accumulation (REA technique. A REA sampler was developed and validated using simultaneous measurements of CO2 fluxes by REA and by eddy correlation. REA measurements were conducted during six campaigns covering spring, summer, and fall between 1997 and 1999. Both uptake and emission of COS and CS2 by the forest were observed, with deposition occurring mainly during the sunlit period and emission mainly during the dark period. On the average, however, the forest acts as a sink for both gases. The average fluxes for COS and CS2 are  -93 ± 11.7 pmol m-2 s-1 and  -18 ± 7.6 pmol m-2 s-1, respectively. The fluxes of both gases appear to be correlated to photosynthetically active radiation and to the CO2 and chem{H_2O} fluxes, supporting the idea that the air-vegetation exchange of both gases is controlled by stomata. An uptake ratio COS/CO2 of 10 ± 1.7 pmol m mol-1 has been derived from the regression line for the correlation between the COS and CO2 fluxes. This uptake ratio, if representative for the global terrestrial net primary production, would correspond to a sink of 2.3 ± 0.5 Tg COS yr-1.

  13. Photooxidation of carbonyl sulfide in the presence of the typical oxides in atmospheric aerosol

    Institute of Scientific and Technical Information of China (English)

    WU; Hongbo; WANG; Xiao; CHEN; Jianmin

    2005-01-01

    Photooxidation of carbonyl sulfide (COS) under UV irradiation and the role of the oxides such as SiO2, Al2O3 and Fe2O3 were investigated by in situ FTIR in a long optical path cell. The major products were identified as SO2 and CO2 by means of IR spectra and GC-MS. SO2 was partially oxidized into SO42- on the surface of the oxides and interior wall of the reactor, which was determined by XPS. The photooxidation is pseudo first order with respect to COS, and the apparent rate constant is approximately 9.30×10-4·s-1. SiO2 and Al2O3 promote the photooxida- tion of COS significantly, but Fe2O3 has no obvious influence on the reaction. The reaction rates in the presence of the oxides or not, rank as: UV + SiO2 > UV + Al2O3 > UV, UV + Fe2O3. The potentiality of the oxides for promoting the photooxidation of COS implicates that the aerosol particles may contribute to the photooxidation of COS in the atmosphere.

  14. Relationships between carbonyl sulfide (COS) and CO2 during leaf gas exchange.

    Science.gov (United States)

    Stimler, Keren; Montzka, Stephen A; Berry, Joseph A; Rudich, Yinon; Yakir, Dan

    2010-06-01

    *Carbonyl sulfide (COS) exchange in C(3) leaves is linked to that of CO(2), providing a basis for the use of COS as a powerful tracer of gross CO(2) fluxes between plants and the atmosphere, a critical element in understanding the response of the land biosphere to global change. *Here, we carried out controlled leaf-scale gas-exchange measurements of COS and CO(2) in representative C(3) plants under a range of light intensities, relative humidities and temperatures, CO(2) and COS concentrations, and following abscisic acid treatments. *No 'respiration-like' emission of COS or detectable compensation point, and no cross-inhibition effects between COS and CO(2) were observed. The mean ratio of COS to CO(2) assimilation flux rates, A(s)/A(c), was c. 1.4 pmol micromol(-1) and the leaf relative uptake (assimilation normalized to ambient concentrations, (A(s)/A(c))(C(a)(c)/C(a)(s))) was 1.6-1.7 across species and conditions, with significant deviations under certain conditions. Stomatal conductance was enhanced by increasing COS, which was possibly mediated by hydrogen sulfide (H(2)S) produced from COS hydrolysis, and a correlation was observed between A(s) and leaf discrimination against C(18)OO. *The results provide systematic and quantitative information necessary for the use of COS in photosynthesis and carbon-cycle research on the physiological to global scales.

  15. Extraction of cobalt(II) from aqueous solution by N,N'-carbonyl difatty amides

    Institute of Scientific and Technical Information of China (English)

    Emad A. Jaffar Al-Mulla; Khalid Waleed S. Al-Janabi

    2011-01-01

    The development of economic and environmentally friendly extractants to recover cobalt metal is required due to the increasing demand for this metal. In this study, solvent extraction of Co(Ⅱ) from aqueous solution using a mixture of N,N'-carbonyl difatty amides (CDFAs) synthesised from palm oil as the extractant was carried out. The effects of various parameters such as acid, contact time, extractant concentration, metal ion concentration and stripping agent and the separation of Co(Ⅱ) from other metal ions such as Fe(Ⅱ), Ni(Ⅱ), Zn(Ⅲ) and Cd(Ⅱ) were investigated. It was found that the extraction of Co(Ⅱ) into the organic phase involved the formation of 1:1 complexes. Co(Ⅱ) was successfully separated from commonly associated metal ions such as Fe(Ⅱ), Ni(Ⅱ), Zn(Ⅲ) and Cd(Ⅱ). Co(Ⅱ) stripping from the loaded organic phase was studied in aqueous solution. These results are useful to recover Co(Ⅱ) from aqueous solution utilising (CDFAs) as an extractant.

  16. Direct 13C-detection for carbonyl relaxation studies of protein dynamics

    Science.gov (United States)

    Pasat, Gabriela; Zintsmaster, John S.; Peng, Jeffrey W.

    2008-08-01

    We describe a method that uses direct 13C-detection for measuring rotating-frame carbonyl ( 13CO) relaxation rates to describe protein functional dynamics. Key advantages of method include the following: (i) unique access to 13CO groups that lack a scalar-coupled 15N- 1H group; (ii) insensitivity to 15N/ 1H exchange-broadening that can derail 1H-detected 15N and HNCO methods; (iii) avoidance of artifacts caused by incomplete water suppression. We demonstrate the approach for both backbone and side-chain 13CO groups. Accuracy of the 13C-detected results is supported by their agreement with those obtained from established HNCO-based approaches. Critically, we show that the 13C-detection approach provides access to the 13CO groups of functionally important residues that are invisible via 1H-detected HNCO methods because of exchange-broadening. Hence, the 13C-based method fills gaps inherent in canonical 1H-detected relaxation experiments, and thus provides a novel complementary tool for NMR studies of biomolecular flexibility.

  17. Selectively fluorinated cyclohexane building blocks: Derivatives of carbonylated all-cis-3-phenyl-1,2,4,5-tetrafluorocyclohexane

    Directory of Open Access Journals (Sweden)

    Mohammed Salah Ayoup

    2015-12-01

    Full Text Available Palladium catalysed carbonylation reactions using the meta- and para-iodo derivatives of all-cis-3-phenyl-1,2,4,5-tetrafluorocyclohexane (4 are illustrated as the start point for a variety of functional group interconversions. The resultant benzaldehyde and benzoic acids offer novel building blocks for further derivatisation and facilitate the incorporation of the facially polarised all-cis-1,2,4,5-tetrafluorocyclohexane motif into more advanced molecular scaffolds.

  18. Obligatory role in GTP hydrolysis for the amide carbonyl oxygen of the Mg(2+)-coordinating Thr of regulatory GTPases.

    Science.gov (United States)

    Zurita, Adolfo; Zhang, Yinghao; Pedersen, Lee; Darden, Tom; Birnbaumer, Lutz

    2010-05-25

    When G-protein alpha subunits binds GTP and Mg(2+), they transition from their inactive to their active conformation. This transition is accompanied by completion of the coordination shell of Mg(2+) with electrons from six oxygens: two water molecules, the ss and gamma phosphoryls of GTP, a helix-alpha1 Ser, and a switch I domain (SWI) Thr, and the repositioning of SWI and SWII domains. SWII binds and regulates effector enzymes and facilitates GTP hydrolysis by repositioning the gamma-carbonyl of a Gln. Mutating the Ser generates regulatory GTPases that cannot lock Mg(2+) into its place and are locked in their inactive state with dominant negative properties. Curiously, mutating the Thr appears to reduce GTP hydrolysis. The reason for this difference is not known because it is also not known why removal of the Thr should affect the overall GTPase cycle differently than removal of the Ser. Working with recombinant Gsalpha, we report that mutating its SWI-Thr to either Ala, Glu, Gln, or Asp results not only in diminished GTPase activity but also in spontaneous activation of the SWII domain. Upon close examination of existing alpha subunit crystals, we noted the oxygen of the backbone carbonyl of SWI-Thr and of the gamma-carbonyl of SWII Gln to be roughly equidistant from the oxygen of the hydrolytic H(2)O. Our observations indicate that the Gln and Thr carbonyls play equihierarchical roles in the GTPase process and provide the mechanism that explains why mutating the Thr mimics mutating the Gln and not that of the Ser.

  19. Microwave Promoted Regeneration of Carbonyl Compounds from Oximes Using N, N-Dichloro Poly(Styrene-co-divinylbenzeneSulphonamide Resin

    Directory of Open Access Journals (Sweden)

    A.G. Beldar

    2011-01-01

    Full Text Available An efficient, economically viable and operationally simple method was developed for deoximation of oximes (of ketones and aldehydes to their corresponding carbonyl compounds using polymer beads of N, N-dichloro poly(styrene-co-divinylbenzenesulphonamide resin. Polymeric reagent offered speedy conversion and substantial yields of products under mild condition and is recyclable. Deoximation was monitored by the use of 13C NMR.

  20. Binding of the 9-O-N-aryl/arylalkyl amino carbonyl methyl substituted berberine analogs to tRNA(phe..

    Directory of Open Access Journals (Sweden)

    Anirban Basu

    Full Text Available BACKGROUND: Three new analogs of berberine with aryl/ arylalkyl amino carbonyl methyl substituent at the 9-position of the isoquinoline chromophore along with berberrubine were studied for their binding to tRNA(phe by wide variety of biophysical techniques like spectrophotometry, spectrofluorimetry, circular dichroism, thermal melting, viscosity and isothermal titration calorimetry. METHODOLOGY/ PRINCIPAL FINDINGS: Scatchard binding isotherms revealed that the cooperative binding mode of berberine was propagated in the analogs also. Thermal melting studies showed that all the 9-O-N-aryl/arylalkyl amino carbonyl methyl substituted berberine analogs stabilized the tRNA(phe more in comparison to berberine. Circular dichroism studies showed that these analogs perturbed the structure of tRNA(phe more in comparison to berberine. Ferrocyanide quenching studies and viscosity results proved the intercalative binding mode of these analogs into the helical organization of tRNA(phe. The binding was entropy driven for the analogs in sharp contrast to the enthalpy driven binding of berberine. The introduction of the aryl/arylalkyl amino carbonyl methyl substituent at the 9-position thus switched the enthalpy driven binding of berberine to entropy dominated binding. Salt and temperature dependent calorimetric studies established the involvement of multiple weak noncovalent interactions in the binding process. CONCLUSIONS/ SIGNIFICANCE: The results showed that 9-O-N-aryl/arylalkyl amino carbonyl methyl substituted berberine analogs exhibited almost ten folds higher binding affinity to tRNA(phe compared to berberine whereas the binding of berberrubine was dramatically reduced by about twenty fold in comparison to berberine. The spacer length of the substitution at the 9-position of the isoquinoline chromophore appears to be critical in modulating the binding affinities towards tRNA(phe.

  1. Bio-orthogonal "click-and-release" donation of caged carbonyl sulfide (COS) and hydrogen sulfide (H2S).

    Science.gov (United States)

    Steiger, Andrea K; Yang, Yang; Royzen, Maksim; Pluth, Michael D

    2017-01-24

    Hydrogen sulfide (H2S) is an important biomolecule with high therapeutic potential. Here we leverage the inverse-electron demand Diels-Alder (IEDDA) click reaction between a thiocarbamate-functionalized trans-cyclooctene and a tetrazine to deliver carbonyl sulfide (COS), which is quickly converted to H2S by the uniquitous enzyme carbonic anhydrase (CA), thus providing a new strategy for bio-orthogonal COS/H2S donation.

  2. A NOVEL COPOLYMER-BOUND CIS- DICARBONYLRHODIUM COMPLEX FOR THE CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    YUAN Guoqing; CHEN Yuying; CHEN Rongyao

    1989-01-01

    A series of porous microspheres of linear and ethylene diacrylate (M ') cross-linked copolymers of 2 - vinylpyridine (V) and methyl acrylate (M) reacted with tetracarbonyldichlorodirhodium to form a series of cis-dicarbonylrhodium chelate complex (MVRh and MVM 'Rh). They are thermally stable yet very reactive in the carbonylation of methanol to acetic acid, and of methanol - acetic acid mixture to acetic acid and acetic anhydride with a selectivity of 100% under relatively mild and anhydrous conditions.

  3. Organic Synthesis in Ionic Liquids: Condensation of 3-Methyl-1-phenyl-5-pyrazolone with Carbonyl Compounds Catalyzed by Ethylenediammonium Diacetate(EDDA)

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    An efficient and environmental benign method is reported for the condensation of 3-methyl-1-phenyl-5-pyrazolone with carbonyl compounds in ionic liquids [Bmim]BF4 and [Bmim]PF6 catalyzed by ethylenediammonium diacetate.

  4. Palladium-catalyzed Carbonylative Cyclization of 2-Bromocyclohex-1-enecarbalde-hydes with Aliphatic Primary Amines Leading to 3-Aminohydroisoindol-1-ones

    Energy Technology Data Exchange (ETDEWEB)

    Bae, Yeon Kyu; Cho, Chan Sik; Yoon, Nam Sik [Kyungpook National Univ., Daegu (Korea, Republic of)

    2013-09-15

    It has been shown that 2-bromocyclohex-1-enecarbaldehydes, which are readily prepared from α-methylene containing cyclohexanones under the bromination conditions of Vilsmeier-Haak reaction, undergo carbonylative cyclization with aliphatic primary amines in the presence of a palladium catalyst and a bidentate phosphorus ligand to give 3-aminohydroisoindol-1-ones. The present reaction provides a promising route for the synthesis of valuable heterocycles from readily available starting ketones. Further study of synthetic applications to heterocycles using these ketones is currently under investigation. Palladium-catalyzed carbonylation of organic halides (or triflates) followed by intramolecular cyclization (carbonyl-ative cyclization) has been widely explored and used as a promising synthetic tool for the construction of the structural core of many pharmacologically and biologically active lactones and lactams.

  5. An Efficient One-pot Synthesis of β-Amino/β-Acetamido Car-bonyl Compounds via ZrCl4-catalyzed Mannich-type Reaction

    Institute of Scientific and Technical Information of China (English)

    SANJEEVA REDDY,Cherkupally; PURNACHANDRA REDDY,Gurrala

    2008-01-01

    Zirconium(IV) chloride catalyzed efficient one-pot synthesis of β-amino/β-acetamido carbonyl compounds at room temperature is described. In the presence of ZrCl4, the three-component Mannich-type reaction via a variety of in situ generated aldimines, with various ketones, aromatic aldehydes and aromatic amines in ethanol, led to the formation of β-amino carbonyl compounds and the four-component Mannich-type reaction of aromatic aldehydes with various ketones, acetonitrile and acetyl chloride resulted in the corresponding β-acetamido carbonyl com-pounds in high to excellent yields. This methodology has also been applied towards the synthesis of dimeric β-amino/β-acetamido carbonyl compounds.

  6. Acetalization of Carbonyl Compounds as Pentaerythritol Diacetals and Diketals in the Presence of Cellulose Sulfuric Acid as an Efficient, Biodegradable and Reusable Catalyst

    Institute of Scientific and Technical Information of China (English)

    Shaterian, Hamid Reza; Rigi, Fatemeh

    2012-01-01

    This paper reports a practical and green method for the acetalization of carbonyl compounds as pentaerythritol diacetals and diketals derivatives using cellulose sulfuric acid as a biodegradable and reusable solid acid catalyst under thermal solvent-free conditions.

  7. Reactivity, Selectivity, and Reaction Mechanisms of Aminoguanidine, Hydralazine, Pyridoxamine, and Carnosine as Sequestering Agents of Reactive Carbonyl Species: A Comparative Study.

    Science.gov (United States)

    Colzani, Mara; De Maddis, Danilo; Casali, Gaia; Carini, Marina; Vistoli, Giulio; Aldini, Giancarlo

    2016-08-19

    Reactive carbonyl species (RCS) are endogenous or exogenous byproducts involved in the pathogenic mechanisms of different oxidative-based disorders. Detoxification of RCS by carbonyl quenchers is a promising therapeutic strategy. Among the most studied quenchers are aminoguanidine, hydralazine, pyridoxamine, and carnosine; their quenching activity towards four RCS (4-hydroxy-trans-2-nonenal, methylglyoxal, glyoxal, and malondialdehyde) was herein analyzed and compared. Their ability to prevent protein carbonylation was evaluated in vitro by using an innovative method based on high-resolution mass spectrometry (HRMS). The reactivity of the compounds was RCS dependent: carnosine efficiently quenched 4-hydroxy-trans-2-nonenal, pyridoxamine was particularly active towards malondialdehyde, aminoguanidine was active towards methylglyoxal and glyoxal, and hydralazine efficiently quenched all RCS. Reaction products were generated in vitro and were characterized by HRMS. Molecular modeling studies revealed that the reactivity was controlled by specific stereoelectronic parameters that could be used for the rational design of improved carbonyl quenchers.

  8. A Novel Sulfided Mo/C Catalyst for Direct Vapor Phase Carbonylation of Methanol at Atmospheric Pressure

    Institute of Scientific and Technical Information of China (English)

    Feng Peng

    2003-01-01

    The direct carbonylation of methanol, without any halide in the feed as a promoter, ispresented. A series of Mo catalysts supported on activated carbon, γ-Al2O3 and SiO2 were prepared.The results show that the support greatly affects the Mo catalyst in the direct vapor-phase carbonylationof methanol, and activated carbon is the best supports of the investigated supports. In addition, therelationships between adsorptions of NH3 and CO and carbonylation of methanol were investigated. A novelsulfided Mo/C catalyst had high activity and selectivity for the vapor phase carbonylation of methanol tomethyl acetate without the addition ofa CH3I promoter to the feed. The reaction conditions were optimizedat a reaction temperature of 573 K, a methanol concentration of 23 mol% and a carbon monoxide spacevelocity of 3,000 L/(kg.h). Under these optimal conditions a methanol conversion of 50%, carbonylationselectivity of 80 mol%, and space-time yield of 8.0 mol/(kg.h) were obtained. The active phase of thisnovel sulfided Mo/C catalyst is the non-crystalline phase, and the active component is present as MoS2.5on the surface of the activated carbon.

  9. Synthesis of ¹⁸O-labeled photosynthetically active chlorophylls at the 3- or 7-carbonyl group with high regioselectivity.

    Science.gov (United States)

    Morishita, Hidetada; Mizoguchi, Tadashi; Tamiaki, Hitoshi

    2010-09-01

    The 3- and 7-formyl groups of chlorophyll-d (Chl-d) and bacteriochlorophyll-e (BChl-e), respectively, were regioselectively labeled with an isotopically stable oxygen-18 (¹⁸O) atom to give 3¹-¹⁸O-labeled Chl-d and 7¹-¹⁸O-labeled BChl-e (ca. 90% ¹⁸O) by exchanging the carbonyl oxygen atoms in the presence of acidic H₂ ¹⁸O (ca. 95% ¹⁸O). Another photosynthetically active chlorophyll, BChl-a possessing the 3-acetyl group was treated under similar acidic conditions to afford a trace amount of 3¹-¹⁸O-labeled BChl-a and further demetallated compound, the corresponding 3¹-¹⁸O-labeled bacteriopheophytin-a as the major product with 55% ¹⁸O-degree. The FT-IR spectra of ¹⁸O-(un)labeled chlorophylls in the solution and the solid states showed that the 3- and 7-carbonyl stretching vibration modes moved to about a 30-cm⁻¹ lower wavenumber by ¹⁸O-labeling at the 3¹- and 7¹-oxo moieties. In artificial chlorosome-like self-aggregates of BChl-e, the ¹⁸O-labeled 7-carbonyl stretching mode was completely resolved from the specially hydrogen-bonded 13-C=O stretching mode, evidently indicating no interaction of the 7-CHO with other functional groups in the supramolecules.

  10. Determination of protein carbonyls in plasma, cell extracts, tissue homogenates, isolated proteins: Focus on sample preparation and derivatization conditions.

    Science.gov (United States)

    Weber, Daniela; Davies, Michael J; Grune, Tilman

    2015-08-01

    Protein oxidation is involved in regulatory physiological events as well as in damage to tissues and is thought to play a key role in the pathophysiology of diseases and in the aging process. Protein-bound carbonyls represent a marker of global protein oxidation, as they are generated by multiple different reactive oxygen species in blood, tissues and cells. Sample preparation and stabilization are key steps in the accurate quantification of oxidation-related products and examination of physiological/pathological processes. This review therefore focuses on the sample preparation processes used in the most relevant methods to detect protein carbonyls after derivatization with 2,4-dinitrophenylhydrazine with an emphasis on measurement in plasma, cells, organ homogenates, isolated proteins and organelles. Sample preparation, derivatization conditions and protein handling are presented for the spectrophotometric and HPLC method as well as for immunoblotting and ELISA. An extensive overview covering these methods in previously published articles is given for researchers who plan to measure protein carbonyls in different samples.

  11. Identification of a functional antioxidant responsive element in the promoter of the Chinese hamster carbonyl reductase 3 (Chcr3) gene.

    Science.gov (United States)

    Miura, Takeshi; Taketomi, Ayako; Nakabayashi, Toshikatsu; Nishinaka, Toru; Terada, Tomoyuki

    2015-07-01

    CHCR3, a member of the short-chain dehydrogenase/reductase superfamily, is a carbonyl reductase 3 enzyme in Chinese hamsters. Carbonyl reductase 3 in humans has been believed to involve the metabolism and/or pharmacokinetics of anthracycline drugs, and the mechanism underlying the gene regulation has been investigated. In this study, the nucleotide sequence of the Chcr3 promoter was originally determined, and its promoter activity was characterised. The proximal promoter region is TATA-less and GC-rich, similar to the promoter region of human carbonyl reductase 3. Cobalt stimulated the transcriptional activity of the Chcr3 gene. The results of a luciferase gene reporter assay demonstrated that cobalt-induced stimulation required an antioxidant responsive element. Forced expression of Nrf2, the transcription factor that binds to antioxidant responsive elements, enhanced the transcriptional activity of the Chcr3 gene. These results suggest that cobalt induces the expression of the Chcr3 gene via the Nrf2-antioxidant responsive element pathway.

  12. Nitric oxide-induced carbonylation of Bcl-2, GAPDH and ANT precedes apoptotic events in insulin-secreting RINm5F cells.

    Science.gov (United States)

    Cahuana, Gladys M; Tejedo, Juan R; Jiménez, Juan; Ramírez, Remedios; Sobrino, Francisco; Bedoya, Francisco J

    2004-02-01

    Generation of high levels of nitric oxide (NO) following induction of NOS2 by interleukin-1 beta (IL-1beta) triggers beta cell apoptosis in insulin-secreting RINm5F cells. Mitochondrial and nuclear events such as downregulation of the antiapoptotic protein Bcl-2, activation of the pore responsible for the permeability transition (PT) and DNA fragmentation are involved in the process. We report in the present paper that exposure of insulin-producing RINm5F cells to NO donors and to IL-1beta leads to oxidative carbonylation of both Bcl-2 and the adenine nucleotide translocator (ANT) component of the mitochondrial PT pore. When the effect of endogenous generation of high concentrations of NO following exposure of cells to IL-1beta was studied, carbonylation of Bcl-2 preceded downregulation of the protein. Overexpression of Mn-SOD decreases substantially the extent of Bcl-2 carbonylation in SIN-1-exposed cells. Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) inhibition, carbonylation and translocation from cytoplasm to nucleus and DNA fragmentation were also induced by DETA/NO exposure. DETA/NO-induced carbonylation of Bcl-2 and ANT proteins takes place 6 h before apoptotic release of histone-associated DNA to cytoplasm. Time course studies also reveal a close parallel between GAPDH translocation to nucleus and carbonylation. Inhibitors of lipooxidation end products formation such as piridoxamine (PM) and aminoguanidine (AG) block NO-triggered carbonylation of Bcl-2, ANT and GAPDH, prevent NO-induced GAPDH enzyme inhibition and nuclear translocation and DNA fragmentation. Our results support the notion that the oxidative carbonylation of proteins plays a role in the control of NO-induced apoptosis.

  13. A Convenient Method for the Oxidation of Alcohols with KMnO_4 to Their Corresponding Carbonyl Compounds in Ionic Liquid Media

    Institute of Scientific and Technical Information of China (English)

    J.Safaei-Ghomi; A.R.Hajipour; A.H.Bamoniri; M.Esmaeili

    2007-01-01

    1 Results Carbonyl compounds constitute an important group of molecules in organic chemistry,which appears in pharmaceuticals,dyes and industrially important chemicals[1-2].The oxidation of alcohols to the corresponding carbonyl groups is a fundamental transformation in organic chemistry and industrially important[3].There is considerable interest in the use of room temperature ionic liquids as promising substitutes for volatile organic solvents.The ambient-temperature ionic liquids,especially those bas...

  14. Eddy covariance carbonyl sulfide flux measurements with a quantum cascade laser absorption spectrometer

    Science.gov (United States)

    Gerdel, Katharina; Spielmann, Felix M.; Hammerle, Albin; Wohlfahrt, Georg

    2016-04-01

    Carbonyl sulfide (COS) is the most abundant sulfur containing trace gas present in the troposphere at concentrations of around 500 ppt. Recent interest in COS by the ecosystem-physiological community has been sparked by the fact that COS co-diffuses into plant leaves pretty much the same way as carbon dioxide (CO2) does, but in contrast to CO2, COS is not known to be emitted by plants. Thus uptake of COS by vegetation has the potential to be used as a tracer for canopy gross photosynthesis, which cannot be measured directly, however represents a key term in the global carbon cycle. Since a few years, quantum cascade laser absorption spectrometers (QCLAS) are commercially available with the precision, sensitivity and time response suitable for eddy covariance (EC) flux measurements. While there exist a handful of published reports on EC flux measurements in the recent literature, no rigorous investigation of the applicability of QCLAS for EC COS flux measurements has been carried out so far, nor have been EC processing and QA/QC steps developed for carbon dioxide and water vapor flux measurements within FLUXNET been assessed for COS. The aim of this study is to close this knowledge gap, to discuss critical steps in the post-processing chain of COS EC flux measurements and to devise best-practice guidelines for COS EC flux data processing. To this end we collected EC COS (and CO2, H2O and CO) flux measurements above a temperate mountain grassland in Austria over the vegetation period 2015 with a commercially available QCLAS. We discuss various aspects of EC data post-processing, in particular issues with the time-lag estimation between sonic anemometer and QCLAS signals and QCLAS time series detrending, as well as QA/QC, in particular flux detection limits, random flux uncertainty, the interaction of various processing steps with common EC QA/QC filters (e.g. detrending and stationarity tests), u*-filtering, etc.

  15. CARIBIC observations of short-lived halocarbons and carbonyl sulphide over Asia

    Science.gov (United States)

    Leedham, E.; Wisher, A.; Oram, D.; Baker, A. K.; Brenninkmeijer, C. A.

    2013-12-01

    The CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container, www.caribic-atmospheric.com) aims to investigate the spatial and temporal distribution of a wide-range of compounds, including those of marine origin/influence, via ~monthly flights to collect in situ data and whole air samples aboard a commercial Lufthansa aircraft. CARIBIC measures up to an altitude of 12 km, allowing the influence of marine compounds on the upper troposphere/lower stratosphere (UTLS) to be explored. In particular, CARIBIC is a useful tool for exploring the impact of very short lived halocarbons (e.g. CH2Br2, CHBr3), whose impact on stratospheric ozone is dependent on convective uplift to the UTLS, a process which is not yet fully quantified. As part of the suite of CARIBIC measurements, whole air samples are analysed at the University of East Anglia (UEA) via gas chromatography mass spectrometry for carbonyl sulphide (OCS) and up to 40 halocarbons (accounting for virtually 100% of organic chlorine, bromine and iodine in the UTLS). Here we present an overview of short-lived halocarbons and OCS measured by CARIBIC. We focus on two regions of particular interest. (1) measurements made in 2012 over the tropical west Pacific to link with UEA measurements made during the SHIVA campaign. (2) measurements made during a collection of flights over India in 2008. Flights over India investigated the impact of monsoon circulation on the distribution of these compounds; for example, elevated concentrations of OCS were seen in CARIBIC samples taken over India during the summer monsoon (July - September). These flights, along with a wider range of flights over Asia (from Frankfurt to Guangzhou, Manila, Bangkok and Kuala Lumpur) can provide unique information on the influence of tropical convection and monsoon circulation on halocarbon and OCS transport within this region.

  16. Temperature dependence of the heterogeneous reaction of carbonyl sulfide on magnesium oxide.

    Science.gov (United States)

    Liu, Yongchun; He, Hong; Ma, Qingxin

    2008-04-03

    The experimental determination of rate constants for atmospheric reactions and how these rate constants vary with temperature remain a crucially important part of atmosphere science. In this study, the temperature dependence of the heterogeneous reaction of carbonyl sulfide (COS) on magnesium oxide (MgO) has been investigated using a Knudsen cell reactor and a temperature-programmed reaction apparatus. We found that the adsorption and the heterogeneous reaction are sensitive to temperature. The initial uptake coefficients (gammat(Ini)) of COS on MgO decrease from 1.07 +/- 0.71 x 10-6 to 4.84 +/- 0.60 x 10-7 with the increasing of temperature from 228 to 300 K, and the steady state uptake coefficients (gammat(SS)) increase from 5.31 +/- 0.06 x 10-8 to 1.68 +/- 0.41 x 10-7 with the increasing of temperature from 240 to 300 K. The desorption rate constants (kdes) were also found to increase slightly with the enhancement of temperature. The empirical formula between the uptake coefficients, desorption rate constants and temperature described in the form of Arrhenius expression were obtained. The activation energies for the heterogeneous reaction and desorption of COS on MgO were measured to be 11.02 +/- 0.34 kJ.mol-1 and 6.30 +/- 0.81 kJ.mol-1, respectively. The results demonstrate that the initial uptake of COS on MgO is mainly contributed by an adsorption process and the steady state uptake is due to a catalytic reaction. The environmental implication was also discussed.

  17. Radiation and atmospheric circulation controls on carbonyl sulfide concentrations in the marine boundary layer

    Science.gov (United States)

    Berkelhammer, M.; Steen-Larsen, H. C.; Cosgrove, A.; Peters, A. J.; Johnson, R.; Hayden, M.; Montzka, S. A.

    2016-11-01

    A potential closure of the global carbonyl sulfide (COS or OCS) budget has recently been attained through a combination of remote sensing, modeling, and extended surface measurements. However, significant uncertainties in the spatial and temporal dynamics of the marine flux still persist. In order to isolate the terrestrial photosynthetic component of the global atmospheric OCS budget, tighter constraints on the marine flux are needed. We present 6 months of nearly continuous in situ OCS concentrations from the North Atlantic during the fall and winter of 2014-2015 using a combination of research vessel and fixed tower measurements. The data are characterized by synoptic-scale ˜100 pmol mol-1 variations in marine boundary layer air during transitions from subtropical to midlatitude source regions. The synoptic OCS variability is shown here to be a linear function of the radiation history along an air parcel's trajectory with no apparent sensitivity to the chlorophyll concentration of the surface waters that the air mass interacted with. This latter observation contradicts expectations and suggests a simple radiation limitation for the combined direct and indirect marine OCS emissions. Because the concentration of OCS in the marine boundary layer is so strongly influenced by an air parcel's history, marine and atmospheric concentrations would rarely be near equilibrium and thus even if marine production rates are held constant at a given location, the ocean-atmosphere flux would be sensitive to changes in atmospheric circulation alone. We hypothesize that changes in atmospheric circulation including latitudinal shifts in the storm tracks could affect the marine flux through this effect.

  18. High winter ozone pollution from carbonyl photolysis in an oil and gas basin

    Science.gov (United States)

    Edwards, Peter M.; Brown, Steven S.; Roberts, James M.; Ahmadov, Ravan; Banta, Robert M.; Degouw, Joost A.; Dubé, William P.; Field, Robert A.; Flynn, James H.; Gilman, Jessica B.; Graus, Martin; Helmig, Detlev; Koss, Abigail; Langford, Andrew O.; Lefer, Barry L.; Lerner, Brian M.; Li, Rui; Li, Shao-Meng; McKeen, Stuart A.; Murphy, Shane M.; Parrish, David D.; Senff, Christoph J.; Soltis, Jeffrey; Stutz, Jochen; Sweeney, Colm; Thompson, Chelsea R.; Trainer, Michael K.; Tsai, Catalina; Veres, Patrick R.; Washenfelder, Rebecca A.; Warneke, Carsten; Wild, Robert J.; Young, Cora J.; Yuan, Bin; Zamora, Robert

    2014-10-01

    The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts

  19. Oxidative carbonylation of phenol with a Pd-O/CeO2-nanotube catalyst

    Institute of Scientific and Technical Information of China (English)

    Ye Yuan; Zhimiao Wang; Hualiang An; Wei Xue; Yanji Wang

    2015-01-01

    CeO2 nanotubes (CeO2-NT) were synthesized using carbon nanotubes as template by a liquid phase deposition and hydrothermal method. X-ray diffraction, transmission electron microscopy, and N2 adsorption-desorption were used to characterize the CeO2-NT. The wall of CeO2-NT was composed of small interconnected nanocrystallites ranging from 4 to 9 nm in size. The specific surface area of CeO2-NT was 108.8 m2/g with an outer diameter of 25 nm and length > 300 nm. Supported Pd cata-lyst, Pd-O/CeO2-NT, was prepared using CeO2-NT as the support. Temperature-programmed reduc-tion analysis showed that the surface oxygen on Pd-O/CeO2-NT could be reduced at low tempera-ture, therefore it showed high activity in the reaction. Pd-O/CeO2-NT was used as the catalyst for the oxidative carbonylation of phenol. It has better activity and DPC selectivity than Pd-O/CeO2-P, which was prepared by supporting Pd on zero dimensional CeO2particles. Under the optimized conditions, phenol conversion was 67.7% with 93.3% DPC selectivity with Pd-O/CeO2-NT. However, its catalyt-ic activity decreased when the catalyst was used for the second time. This was attributed to the destruction of the tubular structure of Pd-O/CeO2-NT and Pd leaching during the reaction.

  20. Observations of the uptake of carbonyl sulfide (COS by trees under elevated atmospheric carbon dioxide concentrations

    Directory of Open Access Journals (Sweden)

    L. Sandoval-Soto

    2012-08-01

    Full Text Available Global change forces ecosystems to adapt to elevated atmospheric concentrations of carbon dioxide (CO2. We understand that carbonyl sulfide (COS, a trace gas which is involved in building up the stratospheric sulfate aerosol layer, is taken up by vegetation with the same triad of the enzymes which are metabolizing CO2, i.e. ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco, phosphoenolpyruvate carboxylase (PEP-Co and carbonic anhydrase (CA. Therefore, we discuss a physiological/biochemical acclimation of these enzymes affecting the sink strength of vegetation for COS. We investigated the acclimation of two European tree species, Fagus sylvatica and Quercus ilex, grown inside chambers under elevated CO2, and determined the exchange characteristics and the content of CA after a 1–2 yr period of acclimation from 350 ppm to 800 ppm CO2. We demonstrate that a compensation point, by definition, does not exist. Instead, we propose to discuss a point of uptake affinity (PUA. The results indicate that such a PUA, the CA activity and the deposition velocities may change and may cause a decrease of the COS uptake by plant ecosystems, at least as long as the enzyme acclimation to CO2 is not surpassed by an increase of atmospheric COS. As a consequence, the atmospheric COS level may rise causing an increase of the radiative forcing in the troposphere. However, this increase is counterbalanced by the stronger input of this trace gas into the stratosphere causing a stronger energy reflection by the stratospheric sulfur aerosol into space (Brühl et al., 2012. These data are very preliminary but may trigger a discussion on COS uptake acclimation to foster measurements with modern analytical instruments.

  1. Quantifying Carbon-Climate Processes at the Regional Scale Using Atmospheric Carbonyl Sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, Elliott [Univ. of California, Merced, CA (United States); Berry, Joe [Carnegie Inst. of Washington, Washington, DC (United States); Torn, Margaret [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); David, Billesbach [Univ. of Nebraska, Lincoln, NE (United States); Seibt, Ulrike [Univ. of California, Los Angeles, CA (United States)

    2013-10-08

    Atmospheric carbonyl sulfide (COS) analysis has the potentially transformative capability for partitioning the regional carbon flux into respiration and photosynthesis components. This emerging approach is based on the observation that continental atmospheric CO2 gradients are dominated by net ecosystem fluxes while continental atmospheric COS gradients are dominated by photosynthesis-related plant uptake. Regional flux partitioning represents a critical knowledge gap due to a lack of robust methods for regional-scale flux partitioning and large uncertainties in forecasting carbon-climate feedbacks. Our completed project characterized the relationship between COS and CO2 surface fluxes using a novel measurement and modeling system in a winter wheat field at the U.S. Department of Energy?s Atmospheric and Radiation Measurement program Central Facility (DOE-ARM CF). The scope of this project included canopy flux measurements, soil flux measurements, regional atmospheric modeling, and analysis of COS and CO2 airborne observations at SGP. Three critical discoveries emerged from this investigation: (1) the new measurement system provided the first field evidence of a robust relationship between COS leaf fluxes and GPP; (2) a previously unknown seasonal soil source of COS was observed and characterized; (3) the regional atmospheric analysis of airborne measurements provided the first COS-based constraints on GPP parameterizations used in earth systems models. Dissemination of these results includes three publications [Billesbach et al., In Press; Campbell et al., In Preparation; Seibt et al., In Review], three presentations at the AGU Fall Meeting (2012), and four invited presentations to department seminars. We have leveraged this foundational project to continue our work on understanding carbon cycle processes at large scales through one funded project (DOE Lab Fee, 2012-2015) and one proposal that is under review (DOE/NASA/USDA/NOAA, 2014-2016).

  2. Synthesis and characterization of neutral and anionic carbonyl derivatives of palladium(II).

    Science.gov (United States)

    Ara, Irene; Forniés, Juan; Martín, Antonio; Martín, L Francisco; Menjón, Babil; Miedes, Helvia

    2010-08-21

    The action of CO on the solvento-complexes cis-[PdR2(thf)2] [R = C6F5 (1), C6Cl5 (2)] at low temperature gives cis-[PdR2(CO)2] [R = C6F5 (3), C6Cl5 (4)] in good yield by simple replacement of the highly labile thf molecules. These are rare cases of Pd(II) dicarbonyl compounds, whose characterization relies on spectroscopic and analytic data. The crystal structure of the square-planar platinum homologue cis-[Pt(C6Cl5)2(CO)2] is also presented. CO can split the double bridging-system in the dinuclear species [{PdR2}2(mu-X)2]2- giving the homologous series of anionic monocarbonyl Pd(II) derivatives with formula [cis-PdR2X(CO)]- (5-10: R = C6F5, C6Cl5; X = Cl, Br, I), which were isolated (except for the R = C6F5 and X = I) and suitably characterized. Characterization includes the crystal and molecular structure of [PPh3Me][cis-Pd(C6F5)2Br(CO)] (6'). The anionic species [NBu4][cis-Pd(C6F5)2Cl(CO)] (5) reacts with neutral cis-[Pd(C6F5)2(CO)2] (3) under CO extrusion, affording the dinuclear derivative [NBu4][{Pd(C6F5)2(CO)}2(mu-Cl)] (11), which contains a single unsupported halide bridge (X-ray diffraction). Complex 11 can be considered as modelling a possible intermediate step in intermolecular CO substitution reactions that are easily undergone by Pd(II) halo carbonyl species.

  3. Soil-atmosphere carbonyl sulfide (COS) exchange in a tropical rainforest at La Selva, Costa Rica

    Science.gov (United States)

    Sun, W.; Maseyk, K. S.; Juarez, S.; Lett, C.; Seibt, U. H.

    2014-12-01

    Carbonyl sulfide (COS) has recently been proposed as a promising tracer for partitioning ecosystem carbon assimilation due to the close analogy between leaf uptake processes of COS and CO2. This emerging framework requires accurate characterization of the source and sink components of COS, including soil fluxes. Here we present the first direct, continuous observations of soil COS fluxes for 4 months at a tropical rainforest, La Selva Biological Station, Costa Rica. Three soil plots with contrasting water content were selected for chamber measurements. Our observations confirmed that soils are principally COS sinks, with daily mean COS fluxes averaged across all chambers ranging from -3 to 0 pmol m-2 s-1. When compared with net ecosystem COS uptake which peaks around -30 pmol m-2 s-1, their contributions should be considered in ecosystem COS balance. We did not find a temperature optimum, but soil COS uptake slightly increased with soil temperature, indicating biotic control on soil COS fluxes. Diurnal cycles of COS fluxes were observed during drying out periods after rain. The diel periodicity of COS fluxes was probably obscured by frequent raining at the site. Diffusional control of soil COS fluxes is shown from increasing soil COS uptake at lower soil water-filled pore space. These confirm that soil COS fluxes are mediated both by soil physical and biological factors. Using a depth-resolved diffusion-reaction model with data-driven enzyme activity parameterization, we simulated the COS fluxes from measured soil environmental variables, consistent with observations. This modeling scheme is useful for separating soil COS fluxes from net ecosystem COS fluxes, which lends support to the emergent COS-based approach of carbon flux partitioning.

  4. Do oceanic emissions account for the missing source of atmospheric carbonyl sulfide?

    Science.gov (United States)

    Lennartz, Sinikka; Marandino, Christa A.; von Hobe, Marc; Cortés, Pau; Simó, Rafel; Booge, Dennis; Quack, Birgit; Röttgers, Rüdiger; Ksionzek, Kerstin; Koch, Boris P.; Bracher, Astrid; Krüger, Kirstin

    2016-04-01

    Carbonyl sulfide (OCS) has a large potential to constrain terrestrial gross primary production (GPP), one of the largest carbon fluxes in the carbon cycle, as it is taken up by plants in a similar way as CO2. To estimate GPP in a global approach, the magnitude and seasonality of sources and sinks of atmospheric OCS have to be well understood, to distinguish between seasonal variation caused by vegetation uptake and other sources or sinks. However, the atmospheric budget is currently highly uncertain, and especially the oceanic source strength is debated. Recent studies suggest that a missing source of several hundreds of Gg sulfur per year is located in the tropical ocean by a top-down approach. Here, we present highly-resolved OCS measurements from two cruises to the tropical Pacific and Indian Ocean as a bottom-up approach. The results from these cruises show that opposite to the assumed ocean source, direct emissions of OCS from the tropical ocean are unlikely to account for the missing source. To reduce uncertainty in the global oceanic emission estimate, our understanding of the production and consumption processes of OCS and its precursors, dimethylsulfide (DMS) and carbon disulphide (CS2), needs improvement. Therefore, we investigate the influence of dissolved organic matter (DOM) on the photochemical production of OCS in seawater by considering analysis of the composition of DOM from the two cruises. Additionally, we discuss the potential of oceanic emissions of DMS and CS2 to closing the atmospheric OCS budget. Especially the production and consumption processes of CS2 in the surface ocean are not well known, thus we evaluate possible photochemical or biological sources by analyzing its covariation of biological and photochemical parameters.

  5. Continuous In-situ Measurements of Carbonyl Sulfide to Constrain Ecosystem Carbon and Water Exchange

    Science.gov (United States)

    Rastogi, B.; Kim, Y.; Berkelhammer, M. B.; Noone, D. C.; Lai, C. T.; Hollinger, D. Y.; Bible, K.; Leen, J. B.; Gupta, M.; Still, C. J.

    2014-12-01

    Understanding the processes that control the terrestrial exchange of carbon and water are critical for examining the role of forested ecosystems in changing climates. A small but increasing number of studies have identified Carbonyl Sulfide (OCS) as a potential tracer for photosynthesis. OCS is hydrolyzed by an irreversible reaction in leaf mesophyll cells that is catalyzed by the enzyme, carbonic anhydrase. Leaf-level field and greenhouse studies indicate that OCS uptake is controlled by stomatal activity and that the ratio of OCS and CO2 uptake is reasonably constant. Existing studies on ecosystem OCS exchange have been based on laboratory measurements or short field campaigns and therefore little information on OCS exchange in a natural ecosystem over longer timescales is available. The objective of this study is to further assess the stability of OCS as a tracer for canopy photosynthesis in an active forested ecosystem and also to assess its utility for constraining transpiration, since both fluxes are mediated by canopy stomatal conductance. An off-axis integrated cavity output spectroscopy analyzer (Los Gatos Research Inc.) was deployed at the Wind River Experimental Forest in Washington (45.8205°N, 121.9519°W). Canopy air was sampled from three heights to measure vertical gradients of OCS within the canopy, and OCS exchange between the forest and the atmosphere. Here we take advantage of simultaneous measurements of the stable isotopologues of H2O and CO2 at corresponding heights as well as NEE (Net Ecosystem Exchange) from eddy covariance measurements to compare GPP (Gross Primary Production) and transpiration estimates from a variety of independent techniques. Our findings seek to allow assessment of the environmental and ecophysicological controls on evapotranspiration rates, which are projected to change in coming decades, and are otherwise poorly constrained.

  6. Determination of bond energies by mass spectrometry. Some transition metal carbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Michels, G.D.

    1979-01-01

    Two groups of transition metal carbonyls have been studied, M(CO)/sub 6/ and M(CO)/sub 5/CS complexes of the Group VIB metals and M/sub 2/(CO)/sub 10/ complexes of the Group VIIB metals. Results for the hexacarbonyl complexes indicate that the measured fragmentation energies are in error by 0.25 +- 0.02 eV per CO produced. This is attributed to excitation of CO to the first vibrational state. Least-squares dissociation energies calculated from corrected data for M(CO)/sub 5/CS complexes indicate that the M--CS bond is 3 to 4 times stronger than the M--CO bonds. Substitution of CS for CO in going from M(CO)/sub 6/ to M(CO)/sub 5/CS weakens the remaining M--CO bonds by an average of 0.2 eV. Previously unreported MnTc(CO)/sub 10/ and TcRe(CO)/sub 10/ are prepared by halide substitution of Tc(CO)/sub 5/Br and Re(CO)/sub 5/Br with Mn(CO)/sub 5//sup -/ and Tc(CO)/sub 5//sup -/, respectively. In the positive ion, metal and mixed-metal decacarbonyls are considered as (CO)/sub 5/M/sup +/--M(CO)/sub 5/ complexes possessing five strong and five weak M--CO bonds. For Mn/sub 2/(CO)/sub 10/ and Re/sub 2/(CO)/sub 10/, M/sup +/--M dissociation energies are 3.0 +- 0.1 and 4.0 +- 0.3 eV, respectively. These energies are 2.5 times greater than those reported for homolytic cleavage to M(CO)/sub 5//sup +/ and M(CO)/sub 5/.

  7. Electromagnetic absorbing property of the flaky carbonyl iron particles by chemical corrosion process

    Science.gov (United States)

    Zheng, Dianliang; Liu, Ting; Zhou, Li; Xu, Yonggang

    2016-12-01

    The flaky carbonyl iron particles (CIPs) were prepared using a milling process at the first step, then the chemical corrosion process was done to optimize the particle shape. The particle morphology was characterized by the scanning electron microscopy, the static magnetic property was evaluated on a vibrating sample magnetometer and X-ray diffraction (XRD) patterns were done to analyze the particle crystal grain structure. The complex permittivity and permeability were measured using a vector network analyzer in the frequency range of 2-18 GHz and the reflection loss (RL) was calculated. The results showed that the saturation magnetization value of the CIPs decreased as the CIPs was corroded to the small flakes in chemical corrosion process. The diffraction peaks of the single α-Fe existed in the XRD pattern of CIPs, and the characteristic peaks was more obvious and the intensity of the diffraction pattern was lower by corrosion. The permittivity and the permeability of the corroded milling CIPs was a little larger than the milling CIPs, it was due to the larger aspect ratio based on the fitting calculation process. At thickness 0.6 mm and 0.8 mm, the corroded milling CIPs composite had the better absorbing property than the other two samples. The frequency band (RL<-5 dB) could be widened to 8.96-18 GHz at 0.6 mm and 5.92-18 GHz at 0.8 mm, and RL less than -8 dB began to exist in 8.96-14.72 GHz at 0.8 mm.

  8. Novel effects of FCCP [carbonyl cyanide p-(trifluoromethoxy)phenylhydrazone] on amyloid precursor protein processing.

    Science.gov (United States)

    Connop, B P; Thies, R L; Beyreuther, K; Ida, N; Reiner, P B

    1999-04-01

    Amyloidogenic processing of the beta-amyloid precursor protein (APP) has been implicated in the pathology of Alzheimer's disease. Because it has been suggested that catabolic processing of the APP holoprotein occurs in acidic intracellular compartments, we studied the effects of the protonophore carbonyl cyanide p-(trifluoromethoxy)phenylhydrazone (FCCP) and the H+-ATPase inhibitor bafilomycin A1 on APP catabolism in human embryonic kidney 293 cells expressing either wild-type or "Swedish" mutant APP. Unlike bafilomycin A1, which inhibits beta-amyloid production in cells expressing mutant but not wild-type APP, FCCP inhibited beta-amyloid production in both cell types. Moreover, the effects of FCCP were independent of alterations in total cellular APP levels or APP maturation, and the concentrations used did not alter either cellular ATP levels or cell viability. Bafilomycin A1, which had no effect on beta-amyloid production in wild-type cells, inhibited endocytosis of fluorescent transferrin, whereas concentrations of FCCP that inhibited beta-amyloid production in these cells had no effect on endosomal function. Thus, in wild-type-expressing cells it appears that the beta-amyloid peptide is not produced in the classically defined endosome. Although bafilomycin A1 decreased beta-amyloid release from cells expressing mutant APP but not wild-type APP, it altered lysosomal function in both cell types, suggesting that in normal cells beta-amyloid is not produced in the lysosome. Although inhibition of beta-amyloid production by bafilomycin A1 in mutant cells may occur via changes in endosomal/lysosomal pH, our data suggest that FCCP inhibits wild-type beta-amyloid production by acting on a bafilomycin A1-insensitive acidic compartment that is distinct from either the endosome or the lysosome.

  9. High winter ozone pollution from carbonyl photolysis in an oil and gas basin.

    Science.gov (United States)

    Edwards, Peter M; Brown, Steven S; Roberts, James M; Ahmadov, Ravan; Banta, Robert M; deGouw, Joost A; Dubé, William P; Field, Robert A; Flynn, James H; Gilman, Jessica B; Graus, Martin; Helmig, Detlev; Koss, Abigail; Langford, Andrew O; Lefer, Barry L; Lerner, Brian M; Li, Rui; Li, Shao-Meng; McKeen, Stuart A; Murphy, Shane M; Parrish, David D; Senff, Christoph J; Soltis, Jeffrey; Stutz, Jochen; Sweeney, Colm; Thompson, Chelsea R; Trainer, Michael K; Tsai, Catalina; Veres, Patrick R; Washenfelder, Rebecca A; Warneke, Carsten; Wild, Robert J; Young, Cora J; Yuan, Bin; Zamora, Robert

    2014-10-16

    The United States is now experiencing the most rapid expansion in oil and gas production in four decades, owing in large part to implementation of new extraction technologies such as horizontal drilling combined with hydraulic fracturing. The environmental impacts of this development, from its effect on water quality to the influence of increased methane leakage on climate, have been a matter of intense debate. Air quality impacts are associated with emissions of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs), whose photochemistry leads to production of ozone, a secondary pollutant with negative health effects. Recent observations in oil- and gas-producing basins in the western United States have identified ozone mixing ratios well in excess of present air quality standards, but only during winter. Understanding winter ozone production in these regions is scientifically challenging. It occurs during cold periods of snow cover when meteorological inversions concentrate air pollutants from oil and gas activities, but when solar irradiance and absolute humidity, which are both required to initiate conventional photochemistry essential for ozone production, are at a minimum. Here, using data from a remote location in the oil and gas basin of northeastern Utah and a box model, we provide a quantitative assessment of the photochemistry that leads to these extreme winter ozone pollution events, and identify key factors that control ozone production in this unique environment. We find that ozone production occurs at lower NOx and much larger VOC concentrations than does its summertime urban counterpart, leading to carbonyl (oxygenated VOCs with a C = O moiety) photolysis as a dominant oxidant source. Extreme VOC concentrations optimize the ozone production efficiency of NOx. There is considerable potential for global growth in oil and gas extraction from shale. This analysis could help inform strategies to monitor and mitigate air quality impacts

  10. Indoor Air Quality Investigations on Particulate Matter, Carbonyls, and Tobacco Specific Nitrosamines

    Science.gov (United States)

    Frey, Sarah E.

    Americans spend upwards of 90% of their time indoors, hence indoor air quality (IAQ) and the impact of IAQ on human health is a major public health concern. IAQ can be negatively impacted by outdoor pollution infiltrating indoors, the emission of indoor pollutants, indoor atmospheric chemistry and poor ventilation. Energy saving measures like retrofits to seal the building envelope to prevent the leakage of heated or cooled air will impact IAQ. However, existing studies have been inconclusive as to whether increased energy efficiency is leading to detrimental IAQ. In this work, field campaigns were conducted in apartment homes in Phoenix, Arizona to evaluate IAQ as it relates to particulate matter (PM), carbonyls, and tobacco specific nitrosamines (TSNA). To investigate the impacts of an energy efficiency retrofit on IAQ, indoor and outdoor air quality sampling was carried out at Sunnyslope Manor, a city-subsidized senior living apartment complex. Measured indoor formaldehyde levels before the building retrofit exceeded reference exposure limits, but in the long term follow-up sampling, indoor formaldehyde decreased for the entire study population by a statistically significant margin. Indoor PM levels were dominated by fine particles and showed a statistically significant decrease in the long term follow-up sampling within certain resident subpopulations (i.e. residents who reported smoking and residents who had lived longer at the apartment complex). Additionally, indoor glyoxal and methylglyoxal exceeded outdoor concentrations, with methylglyoxal being more prevalent pre-retrofit than glyoxal, suggesting different chemical pathways are involved. Indoor concentrations reported are larger than previous studies. TSNAs, specifically N'-nitrosonornicotine (NNN), 4-(methyl-nitrosamino)-4-(3-pyridyl)-butanal (NNA) and 4-(methylnitrosoamino)-1-(3-pyridyl)-1-butanone (NNK) were evaluated post-retrofit at Sunnyslope Manor. Of the units tested, 86% of the smoking units and

  11. Using NDACC column measurements of carbonyl sulfide to estimate its sources and sinks

    Science.gov (United States)

    Wang, Yuting; Marshall, Julia; Palm, Mathias; Deutscher, Nicholas; Roedenbeck, Christian; Warneke, Thorsten; Notholt, Justus; Baker, Ian; Berry, Joe; Suntharalingam, Parvadha; Jones, Nicholas; Mahieu, Emmanuel; Lejeune, Bernard; Hannigan, James; Conway, Stephanie; Strong, Kimberly; Campbell, Elliott; Wolf, Adam; Kremser, Stefanie

    2016-04-01

    Carbonyl sulfide (OCS) is taken up by plants during photosynthesis through a similar pathway as carbon dioxide (CO2), but is not emitted by respiration, and thus holds great promise as an additional constraint on the carbon cycle. It might act as a sort of tracer of photosynthesis, a way to separate gross primary productivity (GPP) from the net ecosystem exchange (NEE) that is typically derived from flux modeling. However the estimates of OCS sources and sinks still have significant uncertainties, which make it difficult to use OCS as a photosynthetic tracer, and the existing long-term surface-based measurements are sparse. The NDACC-IRWG measures the absorption of OCS in the atmosphere, and provides a potential long-term database of OCS total/partial columns, which can be used to evaluate OCS fluxes. We have retrieved OCS columns from several NDACC sites around the globe, and compared them to model simulation with OCS land fluxes based on the simple biosphere model (SiB). The disagreement between the measurements and the forward simulations indicates that (1) the OCS land fluxes from SiB are too low in the northern boreal region; (2) the ocean fluxes need to be optimized. A statistical linear flux model describing OCS is developed in the TM3 inversion system, and is used to estimate the OCS fluxes. We performed flux inversions using only NOAA OCS surface measurements as an observational constraint and with both surface and NDACC OCS column measurements, and assessed the differences. The posterior uncertainties of the inverted OCS fluxes decreased with the inclusion of NDACC data comparing to those using surface data only, and could be further reduced if more NDACC sites were included.

  12. Carbonyl sulfide exchange in soils for better estimates of ecosystem carbon uptake

    Directory of Open Access Journals (Sweden)

    M. E. Whelan

    2015-08-01

    Full Text Available Carbonyl sulfide (COS measurements are one of the emerging tools to better quantify gross primary production (GPP, the largest flux in the global carbon cycle. COS is a gas with a similar structure to CO2; COS uptake is thought to be a proxy for GPP. However, soils are a potential source or sink of COS. This study presents a framework for understanding soil-COS interactions. Excluding wetlands, most of the few observations of isolated soils that have been made show small uptake of atmospheric COS. Recently, a series of studies at an agricultural site in the central United States found soil COS production under hot conditions an order of magnitude greater than fluxes at other sites. To investigate the extent of this phenomenon, soils were collected from 5 new sites and incubated in a variety of soil moisture and temperature states. We found that soils from a desert, an oak savannah, a deciduous forest, and a rainforest exhibited small COS fluxes, behavior resembling previous studies. However, soil from an agricultural site in Illinois, > 800 km away from the initial central US study site, demonstrated comparably large soil fluxes under similar conditions. These new data suggest that, for the most part, soil COS interaction is negligible compared to plant uptake of COS. We present a model that anticipates the large agricultural soil fluxes so that they may be taken into account. While COS air-monitoring data are consistent with the dominance of plant uptake, improved interpretation of these data should incorporate the soil flux parameterizations suggested here.

  13. Carbonyl sulfide exchange in soils for better estimates of ecosystem carbon uptake

    Science.gov (United States)

    Whelan, Mary E.; Hilton, Timothy W.; Berry, Joseph A.; Berkelhammer, Max; Desai, Ankur R.; Campbell, J. Elliott

    2016-03-01

    Carbonyl sulfide (COS) measurements are one of the emerging tools to better quantify gross primary production (GPP), the largest flux in the global carbon cycle. COS is a gas with a similar structure to CO2; COS uptake is thought to be a proxy for GPP. However, soils are a potential source or sink of COS. This study presents a framework for understanding soil-COS interactions. Excluding wetlands, most of the few observations of isolated soils that have been made show small uptake of atmospheric COS. Recently, a series of studies at an agricultural site in the central United States found soil COS production under hot conditions an order of magnitude greater than fluxes at other sites. To investigate the extent of this phenomenon, soils were collected from five new sites and incubated in a variety of soil moisture and temperature states. We found that soils from a desert, an oak savannah, a deciduous forest, and a rainforest exhibited small COS fluxes, behavior resembling previous studies. However, soil from an agricultural site in Illinois, > 800 km away from the initial central US study site, demonstrated comparably large soil fluxes under similar conditions. These new data suggest that, for the most part, soil COS interaction is negligible compared to plant uptake of COS. We present a model that anticipates the large agricultural soil fluxes so that they may be taken into account. While COS air-monitoring data are consistent with the dominance of plant uptake, improved interpretation of these data should incorporate the soil flux parameterizations suggested here.

  14. Variability of atmospheric carbonyl sulfide at a semi-arid urban site in western India.

    Science.gov (United States)

    Mallik, Chinmay; Chandra, Naveen; Venkataramani, S; Lal, Shyam

    2016-05-01

    Atmospheric carbonyl sulfide (COS) is a major precursor for sulfate aerosols that play a critical role in climate regulation. Recent studies have highlighted the importance of COS measurements as a reliable means to constrain biospheric carbon assimilation. In a scenario of limited availability of COS data around the globe, we present gas-chromatographic measurements of atmospheric COS mixing ratios over Ahmedabad, a semi-arid, urban region in western India. These measurements, being reported for the first time over an Indian site, enable us to understand the diurnal and seasonal variation in atmospheric COS with respect to its natural, anthropogenic and photochemical sources and sinks. The annual mean COS mixing ratio over Ahmedabad is found to be 0.83±0.43ppbv, which is substantially higher than free tropospheric values for the northern hemisphere. Inverse correlation of COS with soil and skin temperature, suggests that the dry soil of the semi-arid study region is a potential sink for atmospheric COS. Positive correlations of COS with NO2 and CO during post-monsoon and the COS/CO slope of 0.78pptv/ppbv reveals influence of diesel combustion and tire wear. The highest concentrations of COS are observed during pre-monsoon; COS/CO2 slope of 44.75pptv/ppmv combined with information from air mass back-trajectories reveal marshy wetlands spanning over 7500km(2) as an important source of COS in Ahmedabad. COS/CO2 slopes decrease drastically (8.28pptv/ppmv) during post-monsoon due to combined impact of biospheric uptake and anthropogenic emissions.

  15. Diurnal Fluxes of Carbonyl Sulfide (COS) in a Subtropical Salt Marsh

    Science.gov (United States)

    Whelan, M.; Min, D. H.; Rhew, R. C.; Liu, Y.

    2009-12-01

    The atmospheric sulfur budget has been greatly perturbed, with anthropogenic contributions exceeding natural emissions. Carbonyl sulfide (COS) is the most abundant, longest-lived reduced sulfur compound in the atmosphere, and COS concentration changes could have a significant effect on the global climate and the natural biogeochemical sulfur cycle. Measuring fluxes of COS presents a methodological challenge, and in situ measurements from terrestrial ecosystems are sparse. Terrestrial plants are considered to be the largest sink for COS in the troposphere, although specific species have been reported to act as sources. Here we describe production rates of COS from salt marsh plants on a Texas Gulf coast subtropical barrier island (27.8 °N, 97.1°W). In July 2009, static flux chamber measurements were performed on three sites over the course of 24 hours to capture the temporal and spatial variation of fluxes. Two of the sites were dominated by B. maritima, a common salt marsh plant, while one was a control plot with only marsh soil and no vegetation. Fluxes from the two sites were measured within an hour of each other and showed a very similar pattern with time, indicating that the COS emissions responded to the same environmental factors. Of the environmental parameters measured, fluxes correlated best with soil temperatures at 5 cm depth. The site with the drier of the two soils consistently yielded a 20-30% larger flux. The control plot produced an order of magnitude less COS, but still exhibited a positive flux. These results are part of an ongoing study on how subtropical salt marshes contribute to the global atmospheric sulfur budget.

  16. Carbonyl sulfide exchange in a temperate loblolly pine forest grown under ambient and elevated CO2

    Science.gov (United States)

    White, M. L.; Zhou, Y.; Russo, R. S.; Mao, H.; Talbot, R.; Varner, R. K.; Sive, B. C.

    2010-01-01

    Vegetation, soil and ecosystem level carbonyl sulfide (COS) exchange was observed at Duke Forest, a temperate loblolly pine forest, grown under ambient (Ring 1, R1) and elevated (Ring 2, R2) CO2. During calm meteorological conditions, ambient COS mixing ratios at the top of the forest canopy followed a distinct diurnal pattern in both CO2 growth regimes, with maximum COS mixing ratios during the day (R1=380±4 pptv and R2=373±3 pptv, daytime mean ± standard error) and minimums at night (R1=340±6 pptv and R2=346±5 pptv, nighttime mean ± standard error) reflecting a significant nighttime sink. Nocturnal vegetative uptake (-11 to -21 pmol m-2s-1, negative values indicate uptake from the atmosphere) dominated nighttime net ecosystem COS flux estimates (-10 to -30 pmol m-2s-1) in both CO2 regimes. In comparison, soil uptake (-0.8 to -1.7 pmol m-2 s-1) was a minor component of net ecosystem COS flux. In both CO2 regimes, loblolly pine trees exhibited substantial COS consumption overnight (50% of daytime rates) that was independent of CO2 assimilation. This suggests current estimates of the global vegetative COS sink, which assume that COS and CO2 are consumed simultaneously, may need to be reevaluated. Ambient COS mixing ratios, species specific diurnal patterns of stomatal conductance, temperature and canopy position were the major factors influencing the vegetative COS flux at the branch level. While variability in branch level vegetative COS consumption measurements in ambient and enhanced CO2 environments could not be attributed to CO2 enrichment effects, estimates of net ecosystem COS flux based on ambient canopy mixing ratio measurements suggest less nighttime uptake of COS in R2, the CO2 enriched environment.

  17. Sources and sinks of carbonyl sulfide in an agricultural field in the Southern Great Plains.

    Science.gov (United States)

    Maseyk, Kadmiel; Berry, Joseph A; Billesbach, Dave; Campbell, John Elliott; Torn, Margaret S; Zahniser, Mark; Seibt, Ulli

    2014-06-24

    Net photosynthesis is the largest single flux in the global carbon cycle, but controls over its variability are poorly understood because there is no direct way of measuring it at the ecosystem scale. We report observations of ecosystem carbonyl sulfide (COS) and CO2 fluxes that resolve key gaps in an emerging framework for using concurrent COS and CO2 measurements to quantify terrestrial gross primary productivity. At a wheat field in Oklahoma we found that in the peak growing season the flux-weighted leaf relative uptake of COS and CO2 during photosynthesis was 1.3, at the lower end of values from laboratory studies, and varied systematically with light. Due to nocturnal stomatal conductance, COS uptake by vegetation continued at night, contributing a large fraction (29%) of daily net ecosystem COS fluxes. In comparison, the contribution of soil fluxes was small (1-6%) during the peak growing season. Upland soils are usually considered sinks of COS. In contrast, the well-aerated soil at the site switched from COS uptake to emissions at a soil temperature of around 15 °C. We observed COS production from the roots of wheat and other species and COS uptake by root-free soil up to a soil temperature of around 25 °C. Our dataset demonstrates that vegetation uptake is the dominant ecosystem COS flux in the peak growing season, providing support of COS as an independent tracer of terrestrial photosynthesis. However, the observation that ecosystems may become a COS source at high temperature needs to be considered in global modeling studies.

  18. Soil uptake of carbonyl sulfide in subtropical forests with different successional stages in south China

    Science.gov (United States)

    Yi, Zhigang; Wang, Xinming; Sheng, Guoying; Zhang, Deqiang; Zhou, Guoyi; Fu, Jiamo

    2007-04-01

    The uptake rates of carbonyl sulfide (COS) by soils in subtropical forests with different successional stages were measured using static chambers in Dinghushan Biosphere Reserve (DBR) in south China from July 2004 to March 2005. The three typical tropical forests studied included monsoon evergreen broad-leaf forest (BF), pine and broad-leaf mixed forest (MF) and pine forest (PF), representing forests with different succession stages in the region. COS exchange rates were also compared between the plots with litter-fall remaining (plots L) and those with litter-fall removed (plots S) in each forest. Results showed that these forest soils all acted as sinks for COS with exchange rates of -1.22 to -11.82 pmol m-2 s-1. The MF in the midsuccessional stage had significantly higher uptake rates, and the mean exchange rates in the BF, MF, and PF were -3.90, -4.77, and -3.65 pmol m-2 s-1, respectively. COS uptake rates at plots L were higher than those at plots S. Mean COS fluxes were significantly higher in March (-6.06 pmol m-2 s-1) than those in July (-3.60 pmol m-2 s-1), August (-3.82 pmol m-2 s-1), September (-3.45 pmol m-2 s-1), and October (-3.54 pmol m-2 s-1). Significant correlation was observed between the COS uptake rates and soil respiration rates or microbial biomass, indicating that microbial activity was an important factor controlling the soil uptake of COS. Significant correlations between COS fluxes and initial COS mixing ratios were only observed in the BF and MF. COS fluxes showed no correlation with soil temperature or water content alone in any of the three forests, but do correlate well with soil temperature and water content together in polynomial forms with an order of 2.

  19. Improving North American gross primary production (GPP) estimates using atmospheric measurements of carbonyl sulfide (COS)

    Science.gov (United States)

    Chen, Huilin; Montzka, Steve; Andrews, Arlyn; Sweeney, Colm; Jacobson, Andy; Miller, Ben; Masarie, Ken; Jung, Martin; Gerbig, Christoph; Campbell, Elliott; Abu-Naser, Mohammad; Berry, Joe; Baker, Ian; Tans, Pieter

    2013-04-01

    Understanding the responses of gross primary production (GPP) to climate change is essential for improving our prediction of climate change. To this end, it is important to accurately partition net ecosystem exchange of carbon into GPP and respiration. Recent studies suggest that carbonyl sulfide is a useful tracer to provide a constraint on GPP, based on the fact that both COS and CO2 are simultaneously taken up by plants and the quantitative correlation between GPP and COS plant uptake. We will present an assessment of North American GPP estimates from the Simple Biosphere (SiB) model, the Carnegie-Ames-Stanford Approach (CASA) model, and the MPI-BGC model through atmospheric transport simulations of COS in a receptor oriented framework. The newly upgraded Hybrid Single Particle Lagrangian Integrated Trajectory Model (HYSPLIT) will be employed to compute the influence functions, i.e. footprints, to link the surface fluxes to the concentration changes at the receptor observations. The HYSPLIT is driven by the 3-hourly archived NAM 12km meteorological data from NOAA NCEP. The background concentrations are calculated using empirical curtains along the west coast of North America that have been created by interpolating in time and space the observations at the NOAA/ESRL marine boundary layer stations and from aircraft vertical profiles. The plant uptake of COS is derived from GPP estimates of biospheric models. The soil uptake and anthropogenic emissions are from Kettle et al. 2002. In addition, we have developed a new soil flux map of COS based on observations of molecular hydrogen (H2), which shares a common soil uptake term but lacks a vegetative sink. We will also improve the GPP estimates by assimilating atmospheric observations of COS in the receptor oriented framework, and then present the assessment of the improved GPP estimates against variations of climate variables such as temperature and precipitation.

  20. Vertical Profiles of Carbonyl Sulfide, Halocarbons, and Benzene Over North America

    Science.gov (United States)

    Montzka, S. A.; Calvert, P.; Hall, B.; Elkins, J. W.; Miller, L.; Watson, A.; Sweeney, C.; Tans, P.

    2005-12-01

    A NOAA sampling program to measure vertical profiles of CO{_2}, CH{_4}, N{_2}O, and other gases within the lower atmosphere has been expanded to allow measurements of carbonyl sulfide (COS), CFCs, HCFCs, HFCs, chlorocarbons, bromocarbons, methyl iodide, and benzene. Bimonthly to monthly profiles for these gases have been obtained since September 2004 from flasks collected onboard aircraft at altitudes up to 8 km above sea level at 10 continental and 2 coastal sites in North America. The wide range of gases being measured aid in identifying many different influences on sampled air, such as combustion, input from the oceans, urban emissions, non-urban terrestrial emissions, uptake by vegetation and soils, and vertical mixing. Based upon co-elevated mixing ratios of halocarbons and carbon monoxide or halocarbons and C{_2}Cl{_4}, we anticipate that this sampling program has the potential to provide continental-scale emissions estimates for non-CO{_2} gases that are currently regulated, for example by the Clean Air Act and the Montreal Protocol of Substance that Deplete the Ozone Layer, and for gases listed in the Kyoto Protocol that may be regulated in the future. In addition to the observation of urban pollution and burning plumes, strong and persistent vertical gradients have been observed that vary with season for COS, methyl halides, and chloroform. The results for COS are particularly dramatic, as they show substantially reduced mixing ratios in the continental boundary layer during the growing season. The spatial patterns and seasonality are qualitatively consistent with uptake of COS by photosynthetically active vegetation, though the relative importance of COS loss to soils is poorly constrained. These results will be compared to NOAA ground-based measurements that show strong seasonal variations for COS that are closely tied to those observed for CO{_2}, and the implications of these results on the hypothesis that COS could provide a proxy for gross vegetative

  1. Relationship of photosynthesis to atmospheric carbonyl sulfide for the North American growing season

    Science.gov (United States)

    Campbell, J. E.; Carmichael, G. R.; Chai, T.; Moen, J.; Mena-Carrasco, M.; Tang, Y.; Blake, D. R.; Blake, N. J.; Vay, S. A.; Montzka, S. A.; Collatz, G. J.; Berry, J. A.; Schnoor, J. L.; Stanier, C. O.

    2007-12-01

    Projected changes in climate may reduce the uptake of atmospheric CO2 by terrestrial plants, creating a positive carbon-climate feedback. Our understanding of this feedback is primarily based on global photosynthesis models that were derived from leaf-scale models. It is difficult to validate photosynthesis models with atmospheric CO2 measurements because air depleted of CO2 by photosynthesis mixes with air enriched in CO2 by respiration. It was recently hypothesized that an independent assessment of photosynthesis models could be developed using atmospheric carbonyl sulfide (COS) which is closely related to photosynthesis by COS plant uptake but only has small terrestrial ecosystem sources. Here we report a COS model-observation analysis that is supportive of modeled photosynthesis estimates for the North American growing season. We compared airborne measurements with an atmospheric model driven by COS plant uptake, soil sinks, ocean sources, and anthropogenic sources. The COS plant uptake was calculated by scaling modeled photosynthesis by the plant chamber-derived ratio of photosynthesis to COS plant uptake. Observed and simulated COS concentrations along the flightpaths showed remarkable agreement, both indicating a 13 percent tropospheric drawdown. Modeled COS concentrations were dominated by plant uptake, unlike previous COS models that did not account for the COS-photosynthesis relationship. The model-observation agreement for this plant dominated system corroborates the modeled photosynthesis estimates and the extrapolation of the photosynthesis-COS relationship from plant chamber experiments to our regional atmospheric analysis. We anticipate that our model- observation analysis will be a starting point for using the global observation network9 in a data assimilation framework to constrain climate-photosynthesis sensitivities.

  2. Constraining surface carbon fluxes using in situ measurements of carbonyl sulfide and carbon dioxide

    Science.gov (United States)

    Berkelhammer, M.; Asaf, D.; Still, C.; Montzka, S.; Noone, D.; Gupta, M.; Provencal, R.; Chen, H.; Yakir, D.

    2014-02-01

    Understanding the processes that control the terrestrial exchange of carbon is critical for assessing atmospheric CO2 budgets. Carbonyl sulfide (COS) is taken up by vegetation during photosynthesis following a pathway that mirrors CO2 but has a small or nonexistent emission component, providing a possible tracer for gross primary production. Field measurements of COS and CO2 mixing ratios were made in forest, senescent grassland, and riparian ecosystems using a laser absorption spectrometer installed in a mobile trailer. Measurements of leaf fluxes with a branch-bag gas-exchange system were made across species from 10 genera of trees, and soil fluxes were measured with a flow-through chamber. These data show (1) the existence of a narrow normalized daytime uptake ratio of COS to CO2 across vascular plant species of 1.7, providing critical information for the application of COS to estimate photosynthetic CO2 fluxes and (2) a temperature-dependent normalized uptake ratio of COS to CO2 from soils. Significant nighttime uptake of COS was observed in broad-leafed species and revealed active stomatal opening prior to sunrise. Continuous high-resolution joint measurements of COS and CO2 concentrations in the boundary layer are used here alongside the flux measurements to partition the influence that leaf and soil fluxes and entrainment of air from above have on the surface carbon budget. The results provide a number of critical constraints on the processes that control surface COS exchange, which can be used to diagnose the robustness of global models that are beginning to use COS to constrain terrestrial carbon exchange.

  3. Scaling from Flux Towers to Ecosystem Models: Regional Constraints on GPP from Atmospheric Carbonyl Sulfide

    Science.gov (United States)

    Abu-Naser, M.; Campbell, J.; Berry, J. A.; Seibt, U.; Maseyk, K. S.; Torn, M. S.; Biraud, S. C.; Fischer, M. L.; Billesbach, D. P.; Baker, I. T.; Collatz, G. J.; Chen, H.; Montzka, S. A.; Sweeney, C.

    2012-12-01

    Process-level information on terrestrial carbon fluxes are typically observed at small spatial scales (e.g. eddy flux towers) but critical applications exist at much larger spatial scales (e.g. global ecosystem models). New methodologies are needed to fill this spatial gap. Recent work suggests that analysis of atmospheric carbonyl sulfide (COS) could fill this gap by providing constraints on GPP fluxes at large scales. This proposal is based on evidence that COS plant uptake is quantitatively related to photosynthesis and that COS plant uptake is the dominant COS budget flux influencing atmospheric concentrations over northern extratropical continents. Previous atmospheric analysis of COS has focused on continental or larger scales and only one ecosystem model. Here we explore the spatial and temporal COS variation within North America and their relationship to a range of ecosystem models using regional and global atmospheric transport models. Airborne COS observations are examined from the NOAA-ESRL network including 13 North American airborne sites and a total of 1,447 vertical profiles from years 2004 to 2012. In addition to COS plant uptake, we examined the influence of atmospheric transport treatments, boundary conditions, soil fluxes (mechanistic and empirical), and anthropogenic emissions. The atmospheric COS simulations were consistent with the primary observed spatial and temporal variations in the US mid-continent. This consistency is supportive of ecosystem models because the dominant input for these atmospheric COS simulations is ecosystem model GPP data. However, only the COS simulations driven by a subset of the ecosystem models were able to reproduce the observed COS seasonality in a semiarid cultivated region (ARM/SGP). This subset of ecosystem models produced GPP seasonality that was similar to eddy flux estimates, suggesting a role for COS observations in extending flux tower data to regional spatial scales.

  4. Ecosystem gross CO2 fluxes in a tropical rainforest estimated from carbonyl sulfide (COS)

    Science.gov (United States)

    Seibt, U. H.; Maseyk, K. S.; Lett, C.; Juarez, S.; Sun, W.

    2014-12-01

    Carbonyl sulfide (COS) is a promising new tracer to constrain the gross CO2 fluxes of land ecosystems, particularly in tropical forests where CO2 flux partitioning is often problematic due to the absence of turbulent flow at night. Since vegetation COS and CO2 uptake during photosynthesis is closely coupled, the gross fluxes of photosynthesis and respiration can be quantified through the concurrent measurements of COS and CO2. We measured ecosystem COS and CO2 exchange over four months in a tropical rainforest at La Selva, Costa Rica. We observed a strong ecosystem uptake of COS with a diel signal that was similar but not identical to net CO2 fluxes. Soils at the site mostly acted as COS sinks, correlated with soil moisture. The COS and CO2 data were used to calculate canopy photosynthesis (approx. GPP) from net ecosystem CO2 exchange (NEE) based on the empirical relationship of leaf relative uptake of COS and CO2. Mid-day COS-based GPP estimates ranged from -10 to -15 μmol m-2 s-1, compared to NEE of -5 to -10 μmol m-2 s-1. Ecosystem respiration, calculated as the difference of NEE and GPP, ranged from 5 to 10 μmol m-2 s-1, similar to previous estimates of 5 to 9 μmol m-2 s-1 from CO2 flux partitioning and respiration component measurements at the site. Our results support the application of COS as a new tool in ecosystem flux partitioning that may be particularly useful in tropical forests.

  5. Soil carbonyl sulfide fluxes in a Mediterranean ecosystem: insights from model-data fusion analysis

    Science.gov (United States)

    Sun, W.; Seibt, U. H.; Maseyk, K. S.; Lett, C.

    2013-12-01

    Carbonyl sulfide (COS) is linked to biosphere components of the carbon cycle, due in large part to its hydrolysis by the enzyme carbonic anhydrase (CA). Stomatal diffusion models and observations at leaf and ecosystem scales have demonstrated the potential of COS as a tracer for Gross Primary Production (GPP). Although considered small relative to canopy COS fluxes, accurate knowledge of soil COS fluxes is required for the use of net ecosystem COS fluxes in carbon flux partitioning. However, extensive field measurements of soil COS fluxes are rare and process-based modeling is limited. Here we report continuous chamber measurements of soil COS fluxes in a Mediterranean ecosystem in the Santa Monica Mountains, California during April and early May 2013. Both COS uptake and emissions were observed, but the soil acted as a net sink in most conditions and was a net source only when soil temperatures were above 22 C. COS sink fluxes were positively correlated with soil water content and CO2 fluxes. COS uptake had a maximum at a temperature around 15 C. However, no single environmental variable could be correlated to COS fluxes with an r-square > 0.6. COS fluxes from soil chambers ranged from -9 to 2.5 pmol m-2 s-1. Leaf litter appeared to increase soil COS metabolic activity. We observed huge bursts of soil COS uptake induced by a precipitation event, probably due to enhanced soil microbial activity resulting from alleviated water limitation and a decrease in soil temperature towards the optimum. We used a soil gas exchange model coupled with CA enzyme kinetics to simulate the soil COS fluxes. Micrometeorological and soil data were used to drive the soil flux model. Model simulations indicated that diurnal and synoptic variations of COS fluxes were driven by soil temperature and water content, controlling both CA activity and diffusion. We suggest that multiple parameters need to be optimized to reduce uncertainties in models of soil COS fluxes at larger scales.

  6. Litter dominates surface fluxes of carbonyl sulfide in a Californian oak woodland

    Science.gov (United States)

    Sun, Wu; Maseyk, Kadmiel; Lett, Céline; Seibt, Ulli

    2016-02-01

    Carbonyl sulfide (COS) is a promising tracer for partitioning terrestrial photosynthesis and respiration from net carbon fluxes, based on its daytime co-uptake alongside CO2 through leaf stomata. Because ecosystem COS fluxes are the sum of plant and soil fluxes, using COS as a photosynthesis tracer requires accurate knowledge of soil COS fluxes. At an oak woodland in Southern California, we monitored below-canopy surface (soil + litter) COS and CO2 fluxes for 40 days using chambers and laser spectroscopy. We also measured litter fluxes separately and used a depth-resolved diffusion-reaction model to quantify the role of litter uptake in surface COS fluxes. Soil and litter were primarily COS sinks, and mean surface COS uptake was small (˜1 pmol m-2 s-1). After rainfall, uptake rates were higher (6-8 pmol m-2 s-1), and litter contributed a significant fraction (up to 90%) to surface fluxes. We observed rapid concurrent increases in COS uptake and CO2 efflux following the onset of rain. The patterns were similar to the Birch effect widely documented for soils; however, both COS and CO2 flux increases originated mainly in the litter. The synchronous COS-CO2 litter Birch effect indicates that it results from a rapid increase in litter microbial activity after rainfall. We expect that the drying-rewetting cycles typical for mediterranean and other semiarid ecosystems create a pronounced seasonality in surface COS fluxes. Our results highlight that litter uptake is an important component of surface COS exchange that needs to be taken into account in ecosystem COS budgets and model simulations.

  7. Disentangling Sources and Sinks of Carbonyl Sulfide in a Temperate Mountain Grassland

    Science.gov (United States)

    Wohlfahrt, G.; Hammerle, A.; Kitz, F.; Spielmann, F.

    2015-12-01

    Carbonyl sulfide (COS) is the most abundant sulfur-containing trace gas present in the troposphere at concentrations of around 500 ppt. Recent interest in COS by the ecosystem-physiological community has been sparked by the fact that COS co-diffuses into plant leaves pretty much the same way as carbon dioxide (CO2) does, but in contrast to CO2, COS is not known to be emitted by plants. Thus uptake of COS by vegetation has the potential to be used as a tracer for canopy gross photosynthesis, which cannot be measured directly, however represents a key term in the global carbon cycle. The use of COS as a tracer for canopy gross photosynthesis relies on the assumption that other sinks or sources of COS within an ecosystem are negligible, so that the COS exchange is through leaves only. Here we use concurrent COS and CO2 ecosystem-scale eddy covariance and soil chamber flux measurements together with within and above-canopy concentration profiles and an inverse Lagrangian analysis to disentangle sinks and sources of COS in a temperate mountain grassland. Preliminary results from the vegetation period 2015 suggest the soil at this grassland site to present a source of COS during daytime, which is corroborated by the inverse Lagrangian analysis which infers a COS source in the lowermost part of the canopy, while during nighttime the soil COS exchange is close to zero. At the ecosystem-scale a net uptake of COS was observed throughout the day, which in turn suggests (i) a sink for COS in the plant canopy during nighttime and (ii) a larger (compared to the net flux) gross uptake of COS by the plant canopy during daytime. Taken together our results suggest that using COS as a tracer for canopy gross photosynthesis may be less straight forward than previously thought and that further work is required to better understand the ecosystem-scale COS exchange and its drivers.

  8. Carbonyl sulfide (COS) as a tracer for canopy photosynthesis, transpiration and stomatal conductance: potential and limitations.

    Science.gov (United States)

    Wohlfahrt, Georg; Brilli, Federico; Hörtnagl, Lukas; Xu, Xiaobin; Bingemer, Heinz; Hansel, Armin; Loreto, Francesco

    2012-04-01

    The theoretical basis for the link between the leaf exchange of carbonyl sulfide (COS), carbon dioxide (CO(2)) and water vapour (H(2)O) and the assumptions that need to be made in order to use COS as a tracer for canopy net photosynthesis, transpiration and stomatal conductance, are reviewed. The ratios of COS to CO(2) and H(2)O deposition velocities used to this end are shown to vary with the ratio of the internal to ambient CO(2) and H(2)O mole fractions and the relative limitations by boundary layer, stomatal and internal conductance for COS. It is suggested that these deposition velocity ratios exhibit considerable variability, a finding that challenges current parameterizations, which treat these as vegetation-specific constants. COS is shown to represent a better tracer for CO(2) than H(2)O. Using COS as a tracer for stomatal conductance is hampered by our present poor understanding of the leaf internal conductance to COS. Estimating canopy level CO(2) and H(2)O fluxes requires disentangling leaf COS exchange from other ecosystem sources/sinks of COS. We conclude that future priorities for COS research should be to improve the quantitative understanding of the variability in the ratios of COS to CO(2) and H(2)O deposition velocities and the controlling factors, and to develop operational methods for disentangling ecosystem COS exchange into contributions by leaves and other sources/sinks. To this end, integrated studies, which concurrently quantify the ecosystem-scale CO(2), H(2)O and COS exchange and the corresponding component fluxes, are urgently needed.

  9. Microwave absorbing property of silicone rubber composites with added carbonyl iron particles and graphite platelet

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yonggang; Zhang, Deyuan [Bionic and Micro/Nano/Bio-Manufacturing Technology Research Center, School of Mechanical Engineering and Automation, Beihang University, Beijing 100191 (China); Cai, Jun, E-mail: jun_cai@buaa.edu.cn [Bionic and Micro/Nano/Bio-Manufacturing Technology Research Center, School of Mechanical Engineering and Automation, Beihang University, Beijing 100191 (China); Yuan, Liming; Zhang, Wenqiang [Bionic and Micro/Nano/Bio-Manufacturing Technology Research Center, School of Mechanical Engineering and Automation, Beihang University, Beijing 100191 (China)

    2013-02-15

    Silicone rubber composites filled with carbonyl iron particles (CIPs) and graphite platelet (GP) were prepared using non-coating or coating processes. The complex permittivity and permeability of the composites were measured using a vector network analyzer in the frequency range of 1-18 GHz and dc electric conductivity was measured by the standard four-point contact method. The results showed that CIPs/GP composites fabricated in the coating process had the highest permittivity and permeability due to the particle orientation and interactions between the two absorbents. The coating process resulted in a decreased effective eccentricity of the absorbents, and the dc conductivity increased according to Neelakanta's equations. The reflection loss (RL) value showed that the composites had an excellent absorbing property in the L-band, minimum -11.85 dB at 1.5 mm and -15.02 dB at 2 mm. Thus, GP could be an effective additive in preparing thin absorbing composites in the L-band. - Highlights: Black-Right-Pointing-Pointer The added GP increased the permittivity and permeability of composites filled with CIPs. Black-Right-Pointing-Pointer The enhancement was owing to interactions of the two absorbents and the fabrication process. Black-Right-Pointing-Pointer The coating process decreased the effective eccentricity of the particles, and increased the conductivity of the composites. Black-Right-Pointing-Pointer The composites to which CIPs/GP were added in coating process had excellent absorbing properties in the L-band.

  10. Measurements of C{sub 1}-C{sub 4} carbonyls at forested regions in Mexico

    Energy Technology Data Exchange (ETDEWEB)

    Ceron Breton, J.B.; Padilla, H.; Belmont, R.; Torres, M.C.; Moya, M.; Baez, A.P. [Centro de Ciencias de la Atmosfera, Universidad Nacional Autonoma de Mexico, UNAM, Mexico, D.F. (Mexico)

    2005-04-01

    Measurements of formaldehyde, acetaldehyde, acetone, propionaldehyde and butyraldehyde concentrations were made at five different forested regions in Mexico. One set of two simultaneous samplings was performed at two sites located in the Mexico State, one semi rural area (Temascaltepec), and the other, a forested area (Rancho Viejo). A second set of two simultaneous samplings were made in southern Veracruz State, in one rural area (Monte Pio) and inside a tropical rainforest (at the Biology Station of the University of Mexico). Finally, one sampling was performed in the Sierra of Puebla State (Cuetzalan). Propionaldehyde and butyraldehyde were nor reported because their concentrations were always below or near the detection limit of the technique. The highest concentrations were found from 7:00 to 11:00 and from 11:00 to 19:00 h in all the sampling sites. Arithmetic mean concentrations of acetone were the highest observed among the detected carbonyl compounds in almost all sites, ranging from 0.5 to 8.4 {mu}g m{sup -}3. Arithmetic mean concentrations of formaldehyde and acetaldehyde ranged from 0.83 to 6 {mu}g m{sup -}3 and 0.53 to 4.7 {mu}g m{sup -}3, respectively. The Spearman's correlations between formaldehyde and acetone, and between acetaldehyde and acetone were statistically significant at p<0.05 in almost all sites. A significant correlation (p<0.05) between formaldehyde and acetaldehyde was observed in Mexico State at Rancho Viejo and Temascaltepec. The mean ratio HCHO/CH{sub 3}CHO of concentrations was 1.83 and 1.31 in the forested area of Rancho Viejo, first and second sampling periods, respectively; 1.71 and 1.62 in the semi rural area of Temascaltepec, first and second sampling periods respectively; 1.70 in Cuetzalan; 2.90 in the rural area of Monte Pio; and 1.61 in the Biology Station tropical rainforest. These values show a greater influence of atmospheric pollutants transported from sites with anthropogenic activities, because HCHO/CH{sub 3}CHO

  11. Protein Mediated Oxidative Stress in Patients with Diabetes and its Associated Neuropathy: Correlation with Protein Carbonylation and Disease Activity Markers

    Science.gov (United States)

    Almogbel, Ebtehal

    2017-01-01

    Introduction Free radicals have been implicated as Diabetes Mellitus (DM) contributors in type 2 DM and its associated Diabetes Mellitus Neuropathy (DMN). However, the potential for protein mediated oxidative stress to contribute disease pathogenesis remains largely unexplored. Aim To investigate the status and contribution of protein mediated oxidative stress in patients with DM or DMN and to explore whether oxidative protein modification has a role in DM progression to DM associated neuropathy. Materials and Methods Sera from 42 DM and 37 DMN patients with varying levels of disease activities biomarkers (HbA1C, patients’ age or disease duration) and 21 age- and sex-matched healthy controls were evaluated for serum levels of protein mediated oxidative stress. Results Serum analysis showed significantly higher levels of protein carbonyl contents in both DM and DMN patients compared with healthy controls. Importantly, not only was there an increased number of subjects positive for protein carbonylation, but also the levels of protein carbonyl contents were significantly higher among DM and DMN patients, whose HbA1C were ≥8.8 as compared with patients with lower HbA1C (HbA1Cdiabetes to diabetes neuropathy. Conclusion These findings support an association between protein oxidation and DM or DMN progression. The stronger response observed in patients with higher HbA1C or patients’ ages or disease durations suggests, that protein mediated oxidative stress may be useful in evaluating the progression of DM and its associated DMN and in elucidating the mechanisms of these disorders pathogenesis.

  12. EVA reactive blending with Si-H terminated polysiloxane by carbonyl hydrosilylation reaction: From compatibilised blends to crosslinking networks

    Energy Technology Data Exchange (ETDEWEB)

    Bonnet, J.; Bounor-Legare, V.; Alcouffe, P. [Universite de Lyon, 69003 Lyon (France); Universite de Lyon 1, CNRS UMR5223, Ingenierie des Materiaux Polymeres, 15 Boulevard Latarjet, F-69622 Villeurbanne (France); Cassagnau, P., E-mail: philippe.cassagnau@univ-lyon1.fr [Universite de Lyon, 69003 Lyon (France); Universite de Lyon 1, CNRS UMR5223, Ingenierie des Materiaux Polymeres, 15 Boulevard Latarjet, F-69622 Villeurbanne (France)

    2012-10-15

    A new and original method based on carbonyl hydrosilylation was developed to prepare ethylene-vinyl acetate (EVA)/polysiloxane polymer blends. This focused on the addition of hydrogenosilane groups (SiH) from polysiloxane to the carbonyl groups of EVA. The influence of the nature of the polysiloxane on blend properties was investigated by rheology and scanning electron microscopy. Mixing of a low viscosity polysiloxane with a high viscosity EVA matrix produced a two-phase morphology. The occurrence of the hydrosilylation reaction at the EVA/polysiloxane interface promoted a homogenisation of the blend depending on the molar ratio SiH/vinyl acetate groups, [SiH]/[VA], and the viscosity ratio of the blend. Two distinct behaviours were observed. The formation of a crosslinked network under shear was obtained for a low viscosity ratio between polysiloxane and EVA ({lambda}{sub polysiloxane/EVA} = 4.0 Multiplication-Sign 10{sup -6}) with a high concentration of SiH groups ([SiH]/[VA] = 0.5), while the formation of a compatibilised blend was observed for high molar mass polysiloxanes (Mn > 15,000 g mol{sup -1}) with a low concentration of SiH ([SiH]/[VA] < 4.0 Multiplication-Sign 10{sup -3}). -- Highlights: Black-Right-Pointing-Pointer Carbonyl hydrosilylation reaction was found to enhance EVA/polysiloxane immiscible blends. Black-Right-Pointing-Pointer EVA crosslinking was obtained with a low molar mass polysiloxane. Black-Right-Pointing-Pointer EVA compatibilisation was obtained with a high molar mass polysiloxane. Black-Right-Pointing-Pointer Shear rate was found to improve the hydrosilylation reaction at the interface. Black-Right-Pointing-Pointer A two-phase morphology of the blends was observed after reaction with fine polysiloxane nodules.

  13. Lead-chromium carbonyl complexes incorporated with group 8 metals: synthesis, reactivity, and theoretical calculations.

    Science.gov (United States)

    Shieh, Minghuey; Chu, Yen-Yi; Hsu, Miao-Hsing; Ke, Wei-Ming; Lin, Chien-Nan

    2011-01-17

    The trichromium-lead complex [Pb{Cr(CO)5}3](2-) (1) was isolated from the reaction of PbCl2 and Cr(CO)6 in a KOH/MeOH solution, and the new mixed chromium-iron-lead complex [Pb{Cr(CO)5}{Fe(CO)4}2](2-) (3) was synthesized from the reaction of PbCl2 and Cr(CO)6 in a KOH/MeOH solution followed by the addition of Fe(CO)5. X-ray crystallography showed that 3 consisted of a central Pb atom bound in a trigonal-planar environment to two Fe(CO)4 and one Cr(CO)5 fragments. When complex 1 reacted with 1.5 equiv of Mn(CO)5Br, the Cr(CO)4-bridged dimeric lead-chromium carbonyl complex [Pb2Br2Cr4(CO)18](2-) (4) was produced. However, a similar reaction of 3 or the isostructural triiron-lead complex [Pb{Fe(CO)4}3](2-) (2) with Mn(CO)5Br in MeCN led to the formation of the Fe3Pb2-based trigonal-bipyramidal complexes [Fe3(CO)9{PbCr(CO)5}2](2-) (6) and [Fe3(CO)9{PbFe(CO)4}2](2-) (5), respectively. On the other hand, the Ru3Pb2-based trigonal-bipyramidal complex [Ru3(CO)9{PbCr(CO)5}2](2-) (7) was obtained directly from the reaction of PbCl2, Cr(CO)6, and Ru3(CO)12 in a KOH/MeOH solution. X-ray crystallography showed that 5 and 6 each had an Fe3Pb2 trigonal-bipyramidal core geometry, with three Fe(CO)3 groups occupying the equatorial positions and two PbFe(CO)4 or PbCr(CO)5 units in the axial positions, while 7 displayed a Ru3Pb2 trigonal-bipyramidal geometry with three equatorial Ru(CO)3 groups and two axial PbCr(CO)5 units. The complexes 3-7 were characterized spectroscopically, and their nature, formation, and electrochemistry were further examined by molecular orbital calculations at the B3LYP level of density functional theory.

  14. Global carbonyl sulfide (OCS) measured by MIPAS/Envisat during 2002-2012

    Science.gov (United States)

    Glatthor, Norbert; Höpfner, Michael; Leyser, Adrian; Stiller, Gabriele P.; von Clarmann, Thomas; Grabowski, Udo; Kellmann, Sylvia; Linden, Andrea; Sinnhuber, Björn-Martin; Krysztofiak, Gisèle; Walker, Kaley A.

    2017-02-01

    We present a global carbonyl sulfide (OCS) data set covering the period June 2002 to April 2012, derived from FTIR (Fourier transform infrared) limb emission spectra measured with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on the ENVISAT satellite. The vertical resolution is 4-5 km in the height region 6-15 km and 15 at 40 km altitude. The total estimated error amounts to 40-50 pptv between 10 and 20 km and to 120 pptv at 40 km altitude. MIPAS OCS data show no systematic bias with respect to balloon observations, with deviations mostly below ±50 pptv. However, they are systematically higher than the OCS volume mixing ratios of the ACE-FTS instrument on SCISAT, with maximum deviations of up to 100 pptv in the altitude region 13-16 km. The data set of MIPAS OCS exhibits only moderate interannual variations and low interhemispheric differences. Average concentrations at 10 km altitude range from 480 pptv at high latitudes to 500-510 pptv in the tropics and at northern mid-latitudes. Seasonal variations at 10 km altitude amount to up to 35 pptv in the Northern and up to 15 pptv in the Southern Hemisphere. Northern hemispheric OCS abundances at 10 km altitude peak in June in the tropics and around October at high latitudes, while the respective southern hemispheric maxima were observed in July and in November. Global OCS distributions at 250 hPa (˜ 10-11 km) show enhanced values at low latitudes, peaking during boreal summer above the western Pacific and the Indian Ocean, which indicates oceanic release. Further, a region of depleted OCS amounts extending from Brazil to central and southern Africa was detected at this altitude, which is most pronounced in austral summer. This depletion is related to seasonally varying vegetative uptake by the tropical forests. Typical signatures of biomass burning like the southern hemispheric biomass burning plume are not visible in MIPAS data, indicating that this process is only a minor source of upper

  15. Soil emission and uptake of carbonyl sulfide at a temperate mountain grassland

    Science.gov (United States)

    Kitz, Florian; Hammerle, Albin; Laterza, Tamara; Spielmann, Felix M.; Wohlfahrt, Georg

    2016-04-01

    Flux partitioning, i.e. inferring gross primary productivity (GPP) and ecosystem respiration from the measured net ecosystem carbon dioxide (CO2) exchange, is one uncertainty in modelling the carbon cycle and in times where robust models are needed to assess future global changes a persistent problem. A promising new approach is to derive GPP by measuring carbonyl sulfide (COS), the most abundant sulfur-containing trace gas in the atmosphere, with a mean concentration of about 500 pptv in the troposphere. This is possible because COS and CO2 enter the leaf via a similar pathway and are processed by the same enzyme (carbonic anhydrase). A prerequisite to use COS as a proxy for canopy photosynthesis is a robust estimation of COS sources and sinks in an ecosystem. Past studies described soils either as a sink or source, depending on properties like soil temperature and soil water content. The main aim of this study was to quantify the soil COS exchange and its drivers of a temperate mountain grassland in order to aid the use of COS as tracer for canopy CO2 and water vapor exchange. We conducted a field campaign with a Quantum cascade laser at a temperate mountain grassland to estimate the soil COS fluxes under ambient conditions and while simulating a drought. We used self-built fused silica (i.e. light-transparent) soil chambers to avoid COS emissions from built-in materials and to assess the impact of radiation. Vegetation was removed within the chambers, therefor more radiation reached the soil surface compared to natural conditions. This might be the reason for highly positive fluxes during daytime more similar to agricultural study sites. To further investigate this large soil COS source we conducted within canopy concentration measurements near the soil surface and still recorded fluxes confirming the soil as a COS source during daytime. Results from the drought experiment suggested a strong impact of incoming radiation on soil COS fluxes followed by soil

  16. Soil water content plays an important role in soil-atmosphere exchange of carbonyl sulfide (OCS)

    Science.gov (United States)

    Yi, Zhigang; Behrendt, Thomas; Bunk, Rüdiger; Wu, Dianming; Kesselmeier, Jürgen

    2016-04-01

    Carbonyl sulfide (OCS) is a quite stable gas in the troposphere and is transported up to the stratosphere, where it contributes to the sulfate aerosol layer (Crutzen 1976). The tropospheric concentration seems to be quite constant, indicating a balance between sinks and sources. Recent work by Sandoval-Soto et al. (2005) demonstrated the enormous strength of the vegetation sink and the urgent needs to understand the sinks and sources. The role of soils is a matter of discussion (Kesselmeier et al., 1999; Van Diest and Kesselmeier, 2008; Maseyk et al., 2014; Whelan et al., 2015). To better understand the influence of soil water content and OCS mixing ratio on OCS fluxes, we used an OCS analyzer (LGR COS/CO Analyzer 907-0028, Los Gatos, CA, USA) coupled with automated soil chamber system (Behrendt et al., 2014) to measure the OCS fluxes with a slow drying of four different types of soil (arable wheat soil in Mainz, blueberry soil in Waldstein, spruce soil in Waldstein and needle forest soil in Finland). Results showed that OCS fluxes as well as the optimum soil water content for OCS uptake varied significantly for different soils. The net production rates changed significantly with the soil drying out from 100% to about 5% water holding capacity (WHC), implying that soil water content play an important role in the uptake processes. The production and uptake processes were distinguished by the regression of OCS fluxes under different OCS mixing ratios. OCS compensation points (CP) were found to differ significantly for different soil types and water content, with the lowest CP at about 20% WHC, implying that when estimating the global budgets of OCS, especially for soils fluxes, soil water content should be taken into serious consideration. References Crutzen, P. J. 1976, Geophys. Res. Lett., 3, 73-76. Sandoval-Soto, L. et al., 2005, Biogeosciences, 2, 125-132. Kesselmeier, J. et al., 1999, J. Geophys. Res., 104, 11577-11584. Van Diest, H. and Kesselmeier, J. 2008

  17. Carbonyl sulfide hydrolysis in polar ice cores and the feasibility of recovering a paleoatmospheric history

    Science.gov (United States)

    Nicewonger, M. R.; Aydin, K. M.; Saltzman, E. S.; Fudge, T. J.; Waddington, E. D.; Verhulst, K. R.

    2012-12-01

    Carbonyl sulfide (COS) is the most abundant sulfur gas in the atmosphere with a current tropospheric mean level of 484 parts per trillion [Montzka et al., 2007]. The major sources of COS are biomass burning, oceanic emissions of COS, and the atmospheric oxidation of precursor sulfur compounds CS2 and DMS emitted from the oceans and soils. The major losses of atmospheric COS are uptake by vegetation and soil. The uptake of COS by terrestrial vegetation provides a link between the global budget of COS and the carbon cycle. We measured COS in polar ice cores from four Antarctic sites: Taylor Dome, Siple Dome, South Pole, and West Antarctic Ice Sheet Divide. The COS samples ranged in age from 0.2-42 ky BP. There are large differences between the measurements from the various sites during overlapping time periods. COS levels in ice from the warmer sites (Siple Dome and WAIS-D) are considerably lower than those from the colder sites (Taylor Dome and South Pole). This result suggests that the difference reflects COS loss to hydrolysis within the ice core bubbles. The kinetics of COS hydrolysis in aqueous solution have been studied, but there is no information about reaction rates in ice. A 1-dimensional heat and ice flow model was used to determine the temperature history for each ice core sample. Assuming a pseudo-first order Arrhenius rate equation for COS loss in ice, we can correct each ice core sample for post-depositional COS loss. The temperature histories are used with an objective minimization algorithm to determine the optimal kinetic parameters for COS loss to obtain agreement between ice core measurements from different sites. The results indicate that the ice core data from all sites can be reconciled with a single COS atmospheric history. The uncertainty in this history becomes large in warm ice at longer time scales. This study suggests that reconstructing paleoatmospheric COS will require measurements in ice cores from sites with cold surface temperatures

  18. Synthesis and Thermal Behaviour of Lanthanide Complexes of 4′-[(Cholesterylox y)Carbonyl]-Benzo-15-Crown-5

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Lanthanide complexes of a steroid-substituted benzocrown ether were synthesised . The metal-to-ligand ratio of all the metal complexes is 1∶1. The ligand 4′ -[(cholesteryloxy)carbonyl]-benzo-15-crown-5 is a monotropic liquid cryst al, displaying a cholesteric mesophase. The lanthanide complexes with nitrate co unter-ions form a highly viscous mesophase, decomposing at the clearing point. The transition temperatures change as a function of the lanthanide ion. The corr esponding lanthanide complexes with dodecylsulphate (DOS) counter-ions do not f orm a mesophase. In both cases, the metal complexes have a much lower melting po int than the parent ligand.

  19. Synthesis of a Novel Diamine 4-[(4'-Butoxyphenoxy)carbonyl]-phenyl-3", 5"-diaminobenzoate and Corresponding Polyimides

    Institute of Scientific and Technical Information of China (English)

    Li Gang REN; Xiang Yang LIU; Yi GU

    2006-01-01

    A novel diamine 4-[(4'-butoxyphenoxy)carbonyl]phenyl-3",5"-diaminobenzoate (BCDA)was synthesized from 4-butoxyphenol, 4-hydroxybenzoic acid and 3,5-dinitrobenzoic acid through four main intermediates, and a series of polyimides were also synthesized. All the intermediates and the final product were characterized by FTIR and 1H-NMR. The key step in synthesis route is selective hydrolyzation of two ester groups in 4-butoxyphenyl-4'-acetoxybenzoate, by adjusting the reaction temperature and the concentration of ammonia, shorteding the reaction time. The properties of the novel polyimides, such as the aggregation structures, glass transition temperature,solubility and the pretilt angles, were carried out.

  20. Features of the behavior of 4-amino-5-carboxamido-1,2,3-triazole in multicomponent heterocyclizations with carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Eugene S. Gladkov

    2012-11-01

    Full Text Available Multicomponent reactions involving polyfunctional 4-amino-5-carboxamido-1,2,3-triazole and cyclic carbonyl-containing CH-acids were studied under conventional thermal heating, microwave and ultrasonic irradiation. The features of the reactions studied were discussed and the optimized procedures for the synthesis of final triazolopyrimidines were elaborated. In contrast to the similar MCRs of numerous other aminoazoles, a change of direction of the heterocyclizations in the case of 4-amino-5-carboxamido-1,2,3-triazole was not observed when microwave or thermal heating was substituted by ultrasonication at ambient temperature.

  1. KINETIC STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A NOVEL COPOLYMER- BOUND CIS- DICARBONYLRHODIUM COMPLEX

    Institute of Scientific and Technical Information of China (English)

    CHEN Yuying; YUAN Guoqing; CHEN Rongyao

    1989-01-01

    The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh)coordinated with the ethylene diacrylate (M')crosslinked copolymer of methyl acrylate (M) and 2 - vinylpyridine (V) shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex . Polar solvents can accelerate the reaction .Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system . A mechanism similar to that of soluble rhodium catalyst was proposed .

  2. Solid state reactions of nitrogenous heterocyclic compounds (Ⅱ)——Solid state reactions of indole with carbonyl compounds

    Institute of Scientific and Technical Information of China (English)

    李晓陆; 王永梅; 杜大明; 文忠; 熊国祥; 孟继本

    1997-01-01

    Solid state Michael addition reaction of indole with α,β-unsaturaled carbonyl compounds was carried out,by which a series of compounds containing three different heterocyclic groups binding to one carbon atom were obtained.In the presence of Lewis acid,indole could undergo the solid state condensation reaction with aromatic ketones and aldehydes or quinones.The solid state reaction showed higher selectivity and yield than solution reaction The structures of products were identified by IR,1H NMR,MS,elemental analysis and X-ray crystal analysis.The reaction mechanism was also proposed.

  3. The Development and Application of Two-Chamber Reactors and Carbon Monoxide Precursors for Safe Carbonylation Reactions.

    Science.gov (United States)

    Friis, Stig D; Lindhardt, Anders T; Skrydstrup, Troels

    2016-04-19

    Low molecular weight gases (e.g., carbon monoxide, hydrogen, and ethylene) represent vital building blocks for the construction of a wide array of organic molecules. Whereas experimental organic chemists routinely handle solid and liquid reagents, the same is not the case for gaseous reagents. Synthetic transformations employing such reagents are commonly conducted under pressure in autoclaves or under atmospheric pressure with a balloon setup, which necessitates either specialized equipment or potentially hazardous and nonrecommended installations. Other safety concerns associated with gaseous reagents may include their toxicity and flammability and, with certain gases, their inability to be detected by human senses. Despite these significant drawbacks, industrial processes apply gaseous building blocks regularly due to their low cost and ready availability but nevertheless under a strictly controlled manner. Carbon monoxide (CO) fits with all the parameters for being a gas of immense industrial importance but with severe handling restrictions due to its inherent toxicity and flammability. In academia, as well as research and development laboratories, CO is often avoided because of these safety issues, which is a limitation for the development of new carbonylation reactions. With our desire to address the handling of CO in a laboratory setting, we designed and developed a two-chamber reactor (COware) for the controlled delivery and utilization of stoichiometric amounts of CO for Pd-catalyzed carbonylation reactions. In addition to COware, two stable and solid CO-releasing molecules (COgen and SilaCOgen) were developed, both of which release CO upon activation by either Pd catalysis or fluoride addition, respectively. The unique combination of COware with either COgen or SilaCOgen provides a simple reactor setup enabling synthetic chemists to easily perform safe carbonylation chemistry without the need for directly handling the gaseous reagent. With this technology

  4. Are there missing bond paths in Trimethylenemethane-Iron-tri-carbonyl [(CO)3Fe-(C4H6)] complex?

    OpenAIRE

    Shahbazian, Shant

    2013-01-01

    In a recent paper [J. Organomet. Chem. (2013) doi: 10.1016 /j.jorganchem. 2013.03.047] analyzing the bonding mode of Trimethylenemethane (TMM) with some metal carbonyls, Mousavi and Frenking have declared the absence of bond paths, the so-called missed bond paths, between metal atoms and terminal carbon atoms in several complexes. In this communication, it is first demonstrated that the presupposition of the equivalence of a bond path and a chemical bond within the context of the quantum theo...

  5. The estimation of CO bond length changes in the excited states of transition metal carbonyls

    Science.gov (United States)

    Morrison, Sara L.; Turner, James J.

    1994-01-01

    Advances in vibrational spectroscopy have led to increased knowledge of shortlived excited states. In the case of transition metal carbonyl compounds, time-resolved infrared spectra can be measured directly. The CO energy factored force constants are used to estimate the CO bond length distortions upon excitation. The new empirical relationship rCO = 1.674 - 0.184 ln kCO allows excited states CO bond lenghts to be calculated with a standard deviation of ±0.005 Å. For energy factored systems it is deemed unnecessary to calculate pseudodiatomic frequencies ( vPD) from the potential energy distribution.

  6. A density functional theory investigation of the interaction of the tetraaqua calcium cation with bidentate carbonyl ligands.

    Science.gov (United States)

    Quattrociocchi, Daniel Garcez S; Meuser, Marcos Vinicius Monsores; Ferreira, Glaucio Braga; de M Carneiro, José Walkimar; Stoyanov, Stanislav R; da Costa, Leonardo Moreira

    2017-02-01

    Calcium complexes with bidentate carbonyl ligands are important in biological systems, medicine and industry, where the concentration of Ca(2+) is controlled using chelating ligands. The exchange of two water molecules of [Ca(H2O)6](2+) for one bidentate monosubstituted and homo disubstituted dicarbonyl ligand was investigated using the B3LYP/6-311++G(d,p) method. The ligand substituents NH2, OCH3, OH, CH3, H, F, Cl, CN and NO2 are functional groups with distinct electron-donating and -withdrawing effects that bond directly to the sp(2) C atom of the carbonyl group. The geometry, charge and energy characteristics of the complexes were analyzed to help understand the effects of substituents, spacer length and chelation. Coordination strength was quantified in terms of the enthalpy and free energy of the exchange reaction. The most negative enthalpies were calculated for the coordination of bidentate ligands containing three to five methylene group spacers between carbonyls. The chelate effect contribution was analyzed based on the thermochemistry. The electronic character of the substituent modulates the strength of binding to the metal cation, as ligands containing electron-donor substituents coordinate stronger than those with electron-acceptor substituents. This is reflected in the geometric (bond length and chelating angle), electronic (atomic charges) and energetic (components of the total interacting energy) characteristics of the complexes. Energy decomposition analysis (EDA)-an approach for partitioning of the energy into its chemical origins-shows that the electrostatic component of the coordination is predominant, and yields relevant contribution of the covalent term, especially for the electron-withdrawing substituted ligands. The chelate effect of the bidentate ligands was noticeable when compared with substitution by two monodentate ligands. Graphical abstract The affinity of 18 bidentate carbonyl ligands toward the [Ca(H2O)4](2+) cation is evaluated in

  7. Role of carbonyl reducing enzymes in the phase I biotransformation of the non-steroidal anti-inflammatory drug nabumetone in vitro.

    Science.gov (United States)

    Skarydova, Lucie; Nobilis, Milan; Wsól, Vladimir

    2013-04-01

    1. Nabumetone is a clinically used non-steroidal anti-inflammatory drug, its biotransformation includes major active metabolite 6-methoxy-2-naphtylacetic acid and another three phase I as well as corresponding phase II metabolites which are regarded as inactive. One important biotransformation pathway is carbonyl reduction, which leads to the phase I metabolite, reduced nabumetone. 2. The aim of this study is the determination of the role of a particular human liver subcellular fraction in the nabumetone reduction and the identification of participating carbonyl reducing enzymes along with their stereospecificities. 3. Both subcellular fractions take part in the carbonyl reduction of nabumetone and the reduction is at least in vitro the main biotransformation pathway. The activities of eight cytosolic carbonyl reducing enzymes--CBR1, CBR3, AKR1B1, AKR1B10, AKR1C1-4--toward nabumetone were tested. Except for CBR3, all tested reductases transform nabumetone to its reduced metabolite. AKR1C4 and AKR1C3 have the highest intrinsic clearances. 4. The stereospecificity of the majority of the tested enzymes is shifted to the production of an (+)-enantiomer of reduced nabumetone; only AKR1C1 and AKR1C4 produce predominantly an (-)-enantiomer. This project provides for the first time evidence that seven specific carbonyl reducing enzymes participate in nabumetone metabolism.

  8. iCar-PseCp: identify carbonylation sites in proteins by Monte Carlo sampling and incorporating sequence coupled effects into general PseAAC

    Science.gov (United States)

    Jia, Jianhua; Liu, Zi; Xiao, Xuan; Liu, Bingxiang; Chou, Kuo-Chen

    2016-01-01

    Carbonylation is a posttranslational modification (PTM or PTLM), where a carbonyl group is added to lysine (K), proline (P), arginine (R), and threonine (T) residue of a protein molecule. Carbonylation plays an important role in orchestrating various biological processes but it is also associated with many diseases such as diabetes, chronic lung disease, Parkinson's disease, Alzheimer's disease, chronic renal failure, and sepsis. Therefore, from the angles of both basic research and drug development, we are facing a challenging problem: for an uncharacterized protein sequence containing many residues of K, P, R, or T, which ones can be carbonylated, and which ones cannot? To address this problem, we have developed a predictor called iCar-PseCp by incorporating the sequence-coupled information into the general pseudo amino acid composition, and balancing out skewed training dataset by Monte Carlo sampling to expand positive subset. Rigorous target cross-validations on a same set of carbonylation-known proteins indicated that the new predictor remarkably outperformed its existing counterparts. For the convenience of most experimental scientists, a user-friendly web-server for iCar-PseCp has been established at http://www.jci-bioinfo.cn/iCar-PseCp, by which users can easily obtain their desired results without the need to go through the complicated mathematical equations involved. It has not escaped our notice that the formulation and approach presented here can also be used to analyze many other problems in computational proteomics. PMID:27153555

  9. Effects of Silane Coupling Agent on Microstructure and Mechanical Properties of EPDM/Carbonyl Iron Microwave Absorbing Patch

    Institute of Scientific and Technical Information of China (English)

    FENG Yongbao; QIU Tai; ZHANG Jun; SHEN Chunying

    2006-01-01

    The effects of types and amounts of silane coupling agent on mechanical properties of vulcanized rubber microwave absorbing patch (VRMAP) were studied. The mechanisms of silane coupling agent's effects on mechanical properties of rubber microwave absorbing patch (RMAP) and microwave absorbing patch's ( MAP's ) microstructure were also discussed by using SEM and FT-IR. The experimental resalts show that the tensile strength of RMAP could be increased through adding the filler of carbonyl iron powder (CIP) modified by silane coupling agent. RMAP filled with CIP, which was treated by silane coupling agent KH550, possessed a high tensile strength of 11.5 Mpa, which was 448% more than that of MAP whose filler was not modified by any coupling agent. It was found that the optimal amount of KH550 was 1.0 phr to 100.0 phr carbonyl iron powder. The effects of different modifying techniques on RMAP's mechanical properties were also investigated. It is indicated that MAP whose filler is modified by the wet process has the highest tensile strength, but it is not the optimal modifying technique due to complicated wet process. On the contrary, the dry process was very simple, and VRMAP possessed fairly high mechanical properties, therefore, it was the perfect modifying process.

  10. Nitric oxide enhances desiccation tolerance of recalcitrant Antiaris toxicaria seeds via protein S-nitrosylation and carbonylation.

    Directory of Open Access Journals (Sweden)

    Xuegui Bai

    Full Text Available The viability of recalcitrant seeds is lost following stress from either drying or freezing. Reactive oxygen species (ROS resulting from uncontrolled metabolic activity are likely responsible for seed sensitivity to drying. Nitric oxide (NO and the ascorbate-glutathione cycle can be used for the detoxification of ROS, but their roles in the seed response to desiccation remain poorly understood. Here, we report that desiccation induces rapid accumulation of H(2O(2, which blocks recalcitrant Antiaris toxicaria seed germination; however, pretreatment with NO increases the activity of antioxidant ascorbate-glutathione pathway enzymes and metabolites, diminishes H(2O(2 production and assuages the inhibitory effects of desiccation on seed germination. Desiccation increases the protein carbonylation levels and reduces protein S-nitrosylation of these antioxidant enzymes; these effects can be reversed with NO treatment. Antioxidant protein S-nitrosylation levels can be further increased by the application of S-nitrosoglutathione reductase inhibitors, which further enhances NO-induced seed germination rates after desiccation and reduces desiccation-induced H(2O(2 accumulation. These findings suggest that NO reinforces recalcitrant seed desiccation tolerance by regulating antioxidant enzyme activities to stabilize H(2O(2 accumulation at an appropriate concentration. During this process, protein carbonylation and S-nitrosylation patterns are used as a specific molecular switch to control antioxidant enzyme activities.

  11. Multiple abiotic stress tolerance in Vigna mungo is altered by overexpression of ALDRXV4 gene via reactive carbonyl detoxification.

    Science.gov (United States)

    Singh, Preeti; Kumar, Deepak; Sarin, Neera Bhalla

    2016-06-01

    Vigna mungo (blackgram) is an important leguminous pulse crop, which is grown for its protein rich edible seeds. Drought and salinity are the major abiotic stresses which adversely affect the growth and productivity of crop plants including blackgram. The ALDRXV4 belongs to the aldo-keto reductase superfamily of enzymes that catalyze the reduction of carbonyl metabolites in the cells and plays an important role in the osmoprotection and detoxification of the reactive carbonyl species. In the present study, we developed transgenic plants of V. mungo using Agrobacterium mediated transformation. The transgene integration was confirmed by Southern blot analysis whereas the expression was confirmed by RT-PCR, Western blot and enzyme activity. The T1 generation transgenic plants displayed improved tolerance to various environmental stresses, including drought, salt, methyl viologen and H2O2 induced oxidative stress. The increased aldose reductase activity, higher sorbitol content and less accumulation of the toxic metabolite, methylglyoxal in the transgenic lines under non-stress and stress (drought and salinity) conditions resulted in increased protection through maintenance of better photosynthetic efficiency, higher relative water content and less photooxidative damage. The accumulation of reactive oxygen species was remarkably decreased in the transgenic lines as compared with the wild type plants. This study of engineering multiple stress tolerance in blackgram, is the first report to date and this strategy for trait improvement is proposed to provide a novel germplasm for blackgram production on marginal lands.

  12. Phlorotannins from brown algae (Fucus vesiculosus) inhibited the formation of advanced glycation endproducts by scavenging reactive carbonyls.

    Science.gov (United States)

    Liu, Haiyan; Gu, Liwei

    2012-02-08

    Accumulation of advanced glycation end products (AGEs) in vivo is associated with aging, diabetes, Alzheimer's disease, renal failure, etc. The objective of this study was to investigate the inhibitory effects of brown algae Fucus vesiculosus phlorotannins on the formation of AGEs. F. vesiculosus phlorotannins were extracted using 70% acetone. The resultant extract was fractionated into dichloromethane, ethyl acetate, butanol, and water fractions. The ethyl acetate fraction was further fractionated into four subfractions (Ethyl-F1 to -F4) using a Sephadex LH-20 column. F. vesiculosus acetone extract or fractions significantly inhibited the formation of AGEs mediated by glucose and methylglyoxal in a concentration-dependent manner. The concentrations of F. vesiculosus extracts required to inhibit 50% of albumin glycation (EC(50)) in the bovine serum albumin (BSA)-methylglyoxal assay were lower than those of aminoguanidine (a drug candidate for diabetic complication), except for F. vesiculosus acetone extract and dichloromethane fraction. In the BSA-glucose assay, F. vesiculosus extracts inhibited BSA glycation more than or as effectively as aminoguanidine, except for Ethyl-F3 and -F4. The ethyl acetate fraction and its four subfractions scavenged more than 50% of methylglyoxal in two hours. The hypothesis whether F. vesiculosus phlorotannins scavenged reactive carbonyls by forming adducts was tested. Phloroglucinol, the constituent unit of phlorotannins, reacted with glyoxal and methylglyoxal. Five phloroglucinol-carbonyl adducts were detected and tentatively identified using HPLC-ESI-MS(n).

  13. Temperature dependence of the electromagnetic properties and microwave absorption of carbonyl iron particles/silicone resin composites

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Yingying; Zhou, Wancheng; Qing, Yuchang; Luo, Fa; Zhu, Dongmei

    2015-01-15

    Microwave absorbing composites with thin thickness and wideband absorption were successfully prepared by a spraying method using carbonyl iron particles (CIPs) as absorbers and silicone resin as the matrix. The value of reflection loss (RL) below −5 dB can be obtained in the frequency range of 5.76–18 GHz for the composite with 0.8 mm thickness. The temperature dependence of electromagnetic properties and RL of the composites were investigated. The RL of the composite showed a slight variation when the temperature reached up to 200 °C while decreased at 300 °C. The room temperature RL of the composite did not display significant difference before and after the heat treatment at 300 °C for 10 h; the mechanism was also discussed. - Highlights: • Carbonyl iron particles/silicone resin composites are prepared by a spraying method. • Reflection loss values exceed −5 dB at 5.76–18 GHz for an absorber of 0.8 mm thickness. • The variation of reflection loss was studied from room temperature to 300 °C.

  14. Analysis of 31 Hydrazones of Carbonyl Compounds by RRLC-UV and RRLC-MS(/MS: A Comparison of Methods

    Directory of Open Access Journals (Sweden)

    Soraya de M. Ochs

    2015-01-01

    Full Text Available Aldehydes and ketones are volatile organic compounds (VOC emitted into the atmosphere by a large number of natural and anthropogenic sources. Carbonyl compounds (CC are atmospheric pollutants with known damaging effects for the human’s health. In this work, the separation of 31 carbonyl compounds (CC in their 2,4-dinitrophenylhydrazones form was optimized by rapid resolution liquid chromatography in 9 minutes and simultaneously detected by ultraviolet and mass spectrometry with an APCI(− as ionization source. The mass spectra of hydrazones presented the [M-H]− ions as base peak, but the MS/MS spectra showed fragments related to different structural classes of aldehydes and ketones, representing an important tool to assist structure elucidation of unknown CC in real samples. Multiple reactions monitoring (MRM improved the sensitivity and selectivity for the quantitation method. Analytical parameters using both UV and MS (linearity, determination coefficients, detection limits, and sensitivity were compared. The detection methods are complementary and a powerful analytical tool for the detection and quantitation of CC in complex environmental samples.

  15. Aluminium, carbonyls and cytokines in human nipple aspirate fluids: Possible relationship between inflammation, oxidative stress and breast cancer microenvironment.

    Science.gov (United States)

    Mannello, F; Ligi, D; Canale, M

    2013-11-01

    The human breast is likely exposed to Al (aluminium) from many sources including diet and personal care products. Underarm applications of aluminium salt-based antiperspirant provide a possible long-term source of exposure, especially after underarm applications to shaved and abraded skin. Al research in breast fluids likely reflects the intraductal microenvironment. We found increased levels of aluminium in noninvasively collected nipple aspirate fluids (NAF) from 19 breast cancer patients compared with 16 healthy control subjects (268 vs 131 μg/l, respectively; p Aluminium content and carbonyl levels showed a significant positive linear correlation (r(2) 0.6628, p aluminium salts) we also found a significantly increased levels of pro-inflammatory cytokines (IL-1β, IL-6, IL-12 p70, and TNF-α) and chemoattractant CC and CXC chemokines (IL-8, MIP-1α and MCP-1). In 12 invasive cancer NAF samples we found a significant positive linear correlation among aluminium, carbonyls and pro-inflammatory IL-6 cytokine (Y = 64.79x-39.63, r(2) 0.8192, p aluminium ions in oxidative and inflammatory status perturbations of breast cancer microenvironment, suggesting aluminium accumulation in breast microenvironment as a possible risk factor for oxidative/inflammatory phenotype of breast cells.

  16. Soil atmosphere exchange of carbonyl sulfide (COS) regulated by diffusivity depending on water-filled pore space

    Science.gov (United States)

    van Diest, H.; Kesselmeier, J.

    2008-04-01

    The exchange of carbonyl sulfide (COS) between soil and the atmosphere was investigated for three arable soils from Germany, China and Finland and one forest soil from Siberia for parameterization in the relation to ambient carbonyl sulfide (COS) concentration, soil water content (WC) and air temperature. All investigated soils acted as sinks for COS. A clear and distinct uptake optimum was found for the German, Chinese, Finnish and Siberian soils at 11.5%, 9%, 11.5%, and 9% soil WC, respectively, indicating that the soil WC acts as an important biological and physical parameter for characterizing the exchange of COS between soils and the atmosphere. Different optima of deposition velocities (Vd) as observed for the Chinese, Finnish and Siberian boreal soil types in relation to their soil WC, aligned at 19% in relation to the water-filled pore space (WFPS), indicating the dominating role of gas diffusion. This interpretation was supported by the linear correlation between Vd and bulk density. We suggest that the uptake of COS depends on the diffusivity dominated by WFPS, a parameter depending on soil WC, soil structure and porosity of the soil.

  17. Soil atmosphere exchange of carbonyl sulfide (COS regulated by diffusivity depending on water-filled pore space

    Directory of Open Access Journals (Sweden)

    H. Van Diest

    2008-04-01

    Full Text Available The exchange of carbonyl sulfide (COS between soil and the atmosphere was investigated for three arable soils from Germany, China and Finland and one forest soil from Siberia for parameterization in the relation to ambient carbonyl sulfide (COS concentration, soil water content (WC and air temperature. All investigated soils acted as sinks for COS. A clear and distinct uptake optimum was found for the German, Chinese, Finnish and Siberian soils at 11.5%, 9%, 11.5%, and 9% soil WC, respectively, indicating that the soil WC acts as an important biological and physical parameter for characterizing the exchange of COS between soils and the atmosphere. Different optima of deposition velocities (Vd as observed for the Chinese, Finnish and Siberian boreal soil types in relation to their soil WC, aligned at 19% in relation to the water-filled pore space (WFPS, indicating the dominating role of gas diffusion. This interpretation was supported by the linear correlation between Vd and bulk density. We suggest that the uptake of COS depends on the diffusivity dominated by WFPS, a parameter depending on soil WC, soil structure and porosity of the soil.

  18. Soil atmosphere exchange of Carbonyl Sulfide (COS regulated by diffusivity depending on water-filled pore space

    Directory of Open Access Journals (Sweden)

    H. Van Diest

    2007-10-01

    Full Text Available The exchange of carbonyl sulfide (COS between soil and the atmosphere was investigated for three arable soils from Germany, China and Finland and one forest soil from Siberia for parameterization in the relation to ambient carbonyl sulfide (COS concentration, soil water content (WC and air temperature. All investigated soils acted as significant sinks for COS. A clear and distinct uptake optimum was found for the German, Chinese, Finnish and Siberian soils at 11.5%, 9%, 11.5%, and 9% soil WC, respectively, indicating that the soil WC acts as an important biological and physical parameter for characterizing the exchange of COS between soils and the atmosphere. Different optima of deposition velocities (Vd as observed for the Chinese, Finnish and Siberian boreal soil types in relation to their soil WC, aligned at 19% in relation to the water-filled pore space (WFPS, indicating the dominating role of gas diffusion. This interpretation was supported by the linear correlation between Vd and bulk density. We suggest that the uptake of COS depends on the diffusivity dominated by WFPS, a parameter depending on soil WC, soil structure and porosity of the soil.

  19. On-road emissions of carbonyls from vehicles powered by biofuel blends in traffic tunnels in the Metropolitan Area of Sao Paulo, Brazil

    Science.gov (United States)

    Nogueira, Thiago; Souza, Kely Ferreira de; Fornaro, Adalgiza; Andrade, Maria de Fatima; Carvalho, Lilian Rothschild Franco de

    2015-05-01

    On-road emissions of carbonyls from the current vehicle fleet of Brazil were determined in two experimental campaigns, conducted in traffic tunnels located in the Metropolitan Area of São Paulo (MASP), in southeastern Brazil. Among carbonyl species, formaldehyde and acetaldehyde were the most abundant in all sampling periods. In Brazil, heavy-duty vehicles (HDVs) run on a blend of 95% regular diesel/5% biodiesel from soy, whereas light-duty vehicles (LDVs) run on gasohol (75-80% gasoline/20-25% ethanol) or hydrous ethanol. We found that HDVs showed the highest overall carbonyl emissions, although LDVs were responsible for high emissions of acetaldehyde. In comparison with LDVs in California, which are powered by 90% gasoline/10% ethanol, LDVs in Brazil were found to emit 352% and 263% more formaldehyde and acetaldehyde.

  20. Simultaneous determination of gaseous and particulate carbonyls in air by coupling micellar electrokinetic capillary chromatography with molecular imprinting solid-phase extraction.

    Science.gov (United States)

    Sun, Hui; Lai, Jia-Ping; Fung, Ying Sing

    2014-09-05

    A novel method coupling molecular imprinting solid-phase extraction (MISPE) and micellar electrokinetic capillary chromatography (MEKC) was developed to enable the hourly determination of low level of ambient carbonyls, and study their partition between gaseous phase and particulate phase. With 2,4-dinitroaniline (DNAN) as dummy imprinting template, the unreacted 2,4-Dinitrophenylhydrazine (DNPH) in sampling solution could be removed effectively using MISPE, and an average recovery of 97±5.3% (n=5) for the carbonyl-DNPH derivatives was achieved. Owing to the high enrichment due to sample clean-up, and the improvement of MEKC separation efficiency, many low abundant carbonyls could be detected by hourly in the field study.

  1. Scaling up carbonyl sulfide (COS) fluxes from leaf and soil to the canopy

    Science.gov (United States)

    Yang, Fulin; Yakir, Dan

    2016-04-01

    Carbonyl sulfide (COS) with atmospheric concentrations around 500 ppt is an analog of CO2 which can potentially serve as powerful and much needed tracer of photosynthetic CO2 uptake, and global gross primary production (GPP). However, questions remain regarding the application of this approach due to uncertainties in the contributions of different ecosystem components to the canopy scale fluxes of COS. We used laser quantum cascade spectroscopy in combination with soil and branch chambers, and eddy covariance measurements of net ecosystem exchange fluxes of COS and CO2 (NEE) in citrus orchard during the driest summer month to test our ability to integrate the chamber measurements into the ecosystem fluxes. The results indicated that: 1) Soil fluxes showed clear gradient from continuous uptake under the trees in wet soil of up to -4 pmol m-2s-1 (CO2 emission of ~0.5 umol m-2s-1) to emission in dry hot and exposed soil between rows of trees of up to +3 pmol m-2s-1 (CO2 emission of ~11 umol m-2s-1). In all cases a clear correlation between fluxes and soil temperature was observed. 2) At the leaf scale, midday uptake was ~5.5 pmol m-2s-1 (CO2 uptake of ~1.8 umol m-2s-1). Some nighttime COS uptake was observed in the citrus leaves consistent with nocturnal leaf stomatal conductance. Leaf relative uptake (LRU) of COS vs. CO2 was not constant over the diurnal cycle, but showed exponential correlation with photosynthetically active radiation (PAR) during the daytime. 3) At the canopy scale mid-day summer flux reached -12.0 pmol m-2s-1 (NEE ~6 umol m-2s-1) with the diurnal patterns of COS fluxes following those of CO2 fluxes during the daytime, but with small COS uptake fluxes maintained also during the night when significant CO2 emission fluxes were observed. The canopy-scale fluxes always indicated COS uptake, irrespective of the soil emission effects. GPP estimates were consistent with conventional indirect estimates based on NEE and nocturnal measurements. Scaling up

  2. Spectroscopic and theoretical investigations of vibrational frequencies in binary unsaturated transition-metal carbonyl cations, neutrals, and anions.

    Science.gov (United States)

    Zhou, M; Andrews, L; Bauschlicher, C W

    2001-07-01

    Figure 18 presents the C-O stretching vibrational frequencies of the first-row transition-metal monocarbonyl cations, neutrals, and anions in solid neon; similar diagrams have been reported for neutral MCO species in solid argon, but three of the early assignments have been changed by recent work and one new assignment added. The laser-ablation method produces mostly neutral atoms with a few percent cations and electrons for capture to make anions; in contrast, thermal evaporation gives only neutral species. Hence, the very recent neon matrix investigations in our laboratory provide carbonyl cations and anions for comparison to neutrals on a level playing field. Several trends are very interesting. First, for all metals, the C-O stretching frequencies follow the order cations > neutrals > anions with large diagnostic 100-200 cm-1 separations, which is consistent with the magnitude of the metal d to CO pi * donation. Second, for a given charge, there is a general increase in C-O stretching vibrational frequencies with increasing metal atomic number, which demonstrates the expected decrease in the metal to CO pi * donation with increasing metal ionization potential. Some of the structure in this plot arises from the extra stability of the filled and half-filled d shell and from the electron pairing that occurs at the middle of the TM row; the plot resembles the "double-humped" graph found for the variation in properties across a row of transition metals. For the anions, the variation with metal atom is the smallest since all of the metals can easily donate charge to the CO ligand. Third, for the early transition-metal Ti, V, and Cr families, the C-O stretching frequencies decrease when going down the family, but the reverse relationship is observed for the late transition-metal Fe, Co, and Ni families. In most of the present discussion, we have referred to neon matrix frequencies; however, the argon matrix frequencies are complementary, and useful information can be

  3. A High Resolution/Accurate Mass (HRAM) Data-Dependent MS3 Neutral Loss Screening, Classification, and Relative Quantitation Methodology for Carbonyl Compounds in Saliva

    Science.gov (United States)

    Dator, Romel; Carrà, Andrea; Maertens, Laura; Guidolin, Valeria; Villalta, Peter W.; Balbo, Silvia

    2016-10-01

    Reactive carbonyl compounds (RCCs) are ubiquitous in the environment and are generated endogenously as a result of various physiological and pathological processes. These compounds can react with biological molecules inducing deleterious processes believed to be at the basis of their toxic effects. Several of these compounds are implicated in neurotoxic processes, aging disorders, and cancer. Therefore, a method characterizing exposures to these chemicals will provide insights into how they may influence overall health and contribute to disease pathogenesis. Here, we have developed a high resolution accurate mass (HRAM) screening strategy allowing simultaneous identification and relative quantitation of DNPH-derivatized carbonyls in human biological fluids. The screening strategy involves the diagnostic neutral loss of hydroxyl radical triggering MS3 fragmentation, which is only observed in positive ionization mode of DNPH-derivatized carbonyls. Unique fragmentation pathways were used to develop a classification scheme for characterizing known and unanticipated/unknown carbonyl compounds present in saliva. Furthermore, a relative quantitation strategy was implemented to assess variations in the levels of carbonyl compounds before and after exposure using deuterated d 3 -DNPH. This relative quantitation method was tested on human samples before and after exposure to specific amounts of alcohol. The nano-electrospray ionization (nano-ESI) in positive mode afforded excellent sensitivity with detection limits on-column in the high-attomole levels. To the best of our knowledge, this is the first report of a method using HRAM neutral loss screening of carbonyl compounds. In addition, the method allows simultaneous characterization and relative quantitation of DNPH-derivatized compounds using nano-ESI in positive mode.

  4. Electromagnetic and microwave absorbing properties of carbonyl iron/BaTiO{sub 3} composite absorber for matched load of isolator

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Xiaohu [Southwest Institute of Applied Magnetics, Mianyang 621000 (China); Cheng, Yankui [Department of Manufacturing Engineering, Yibin Vocational and Technical College, Yibin 644003 (China)

    2015-11-01

    Composite absorbers made from carbonyl iron powder and BaTiO{sub 3} were prepared by blending technique with the matrix of epoxy resin. The structure and microtopography of the carbonyl iron and BaTiO{sub 3} particles were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The microstructure and electromagnetic properties of the as-prepared composites were investigated by SEM and vector network analyzer (VNA). The effect of the mass ratio of BaTiO{sub 3}/carbonyl iron on the electromagnetic properties of the composites is investigated. The bandwidth with an absorption loss exceeding 30 dB is obtained in the whole measured frequency range for all composites, and an optimal reflection loss drop below 1.5 dB with 24 wt% BaTiO{sub 3}. It is found that the carbonyl iron/BaTiO{sub 3} composite absorber can be a promising candidate as a matched load for the isolator. - Highlights: • Composite absorbers made from carbonyl iron powder and BaTiO3 were prepared by blending technique with the matrix of epoxy resin. • The microwave absorption properties of composites were measured by stripline method. • The bandwidth with an absorption loss exceeding 30 dB is obtained in the whole measured frequency range for all composites, and an optimal reflection loss drop below 1.5 dB with 24 wt% BaTiO{sub 3}. • It is found that the carbonyl iron/BaTiO{sub 3} composite absorber can be a promising candidate as a matched load for the isolator.

  5. (Pyridine)(tetrahydroborato)zinc complex, (Zn(BH{sub 4}){sub 2}(py)), as a new stable, efficient and chemoselective reducing agent for reduction of carbonyl compounds

    Energy Technology Data Exchange (ETDEWEB)

    Zeynizadeh, Behzad; Faraji, Fariba [Urima Univ., Urima (Iran, Islamic Republic of)

    2003-04-01

    (Pyridine)(tetrahydroborato)zinc complex, (Zn(BH{sub 4}){sub 2}(py)), as a stable white solid, was prepared quantitatively by complexation of an equimolar amount of zinc tetrahydroborate and pyridine at room temperature. This reagent can easily reduce variety of carbonyl compounds such as aldehydes, ketones, acyloins, {alpha}-diketones and {alpha},{beta}-unsaturated carbonyl compounds to their corresponding alcohols in good to excellent yields. Reduction reactions were performed in ether or THF at room temperature or under reflux conditions. In addition, the chemoselective reduction of aldehydes over ketones was accomplished successfully with this reducing agent.

  6. 乙醇在新型Mo/C催化剂上的气相羰基化反应%Vapor Phase Carbonylation of Ethanol over Novel Mo/C Catalyst

    Institute of Scientific and Technical Information of China (English)

    何红运; 彭峰

    2000-01-01

    @@ The carbonylation of alcohol to acid or ester is an important process in the chemical industry. The Monsanto process for acetic acid via the homoge neous carbonylation of methanol is an example of the largest scale commercial application of this route[1].Recently, ethanol carbonylation for manufacturing propionic acid and ethyl propionate became an at tractive approach, and many research efforts were made for an appropriate catalyst to carry out the va por phase carbonylation under atmospheric pres sure[2~4]. Although an iodide-promoted Ni/C cata lyst is found to exhibit satisfactory activity and se lectivity for the vapor phase carbonylation of ethanol, it is affected by the disadvantages associat ed with a highly corrosive reaction medium and dif ficult product separation owing to the use of ethyl iodide as promoter. There has been little success in finding heterogeneous or homogeneous catalyst that can operate effectively without a halide promoter[5].

  7. Removal of carbonyl sulfide from CO2 stream using AgNO3-modified NaZSM-5

    Institute of Scientific and Technical Information of China (English)

    Yanjun; Wang; Shaoyun; Chen; Heng; Chen; Xingzhou; Yuan; Yongchun; Zhang

    2013-01-01

    Removal of carbonyl sulfide(COS) from CO2 stream is significant for the production and utilization of food grade CO2. This study investigates the adsorption performance of Ag/NaZSM-5 as adsorbent prepared by incipient wetness impregnation for the removal of COS from a CO2 stream in a fixed-bed adsorption apparatus. Effects of various conditions on the preparation of adsorbent, adsorption and desorption were intensively examined. The results revealed that COS can be removed to below 1×10-9from a CO2stream(1000 ppm COS/CO2) using Ag/NaZSM-5(10 wt% AgNO3) with an adsorption capacity of 12.86 mg·g-1. The adsorbent can be fully regenerated using hot air at 450 C. The adsorption ability remained stable even after eight cycles of regeneration.

  8. Na@SiO2-Mediated Addition of Organohalides to Carbonyl Compounds for the Formation of Alcohols and Epoxides

    Science.gov (United States)

    Kapoor, Mohit; Hwu, Jih Ru

    2016-11-01

    Alcohols and epoxides were generated by the addition of organohalides to carbonyl compounds in the presence of sodium metal impregnated with silica gel (Na@SiO2) in THF at 25 °C through a radical pathway. Under the same conditions, Schiff bases were also successfully converted to the corresponding amines. Furthermore, the reaction of aldehydes with α-haloesters or 4-(chloromethyl)-coumarin with the aid of Na@SiO2 generated trans epoxides. An unprecedented mechanism is proposed for their formation. The advantages associated with these new reactions include: (1) products are obtained in good-to-excellent yields, (2) reactions are completed at room temperatures in a short period of time (<2.0 h), (3) it is unnecessary to perform the reactions under anhydrous conditions, and (4) the entire process requires only simple manipulations.

  9. Carbonyl(N-nitroso-N-oxido-1-naphtylamine-κ2O,O′(triphenylphosphine-κPrhodium(I acetone solvate

    Directory of Open Access Journals (Sweden)

    T. J. Muller

    2009-12-01

    Full Text Available The title compound, [Rh(C10H7N2O2(C18H15P(CO]·(CH32CO, is the second structural report of a metal complex formed with the O,O′-C10H7N2O2 (neocupferrate ligand. In the crystal structure, the metal centre is surrounded by one carbonyl ligand, one triphenylphosphine ligand and the bidentate neocupferrate ligand, forming a distorted square-planar RhCO2P coordination set which is best illustrated by the small O—Rh—O bite angle of 77.74 (10°. There are no classical hydrogen-bond interactions observed for this complex.

  10. Cloning and expression of the gene encoding (R)-specific carbonyl reductase from Candida parapsilosis CCTCC M203011

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The gene which encodes (R)-specific carbonyl reductase (rCR) from Candida parapsilosis CCTCC M203011 was cloned, sequenced and compared with genes from the GenBank. The results indicated that rCR gene was 1011 bp, encoding a protein of 336 amino acids with a molecular weight of 35.9 kDa, and its nucleotide sequence showed 99% similarity to those of other members of the alcohol dehydrogenase superfamily. The rCR gene could express in recombinant strain Escherichia coli JM 109, and the expression plasmid could produce (R)-1-pheny-1,2-ethanediol (100% e.e., 80.14% yield) fromβ-hydroxyacetophenone without any additive to regenerate NAD+ from NADH.

  11. Carbonyl cyanide p-trifluoromethoxyphenylhydrazone (FCCP) induces initiation factor 2 alpha phosphorylation and translation inhibition in PC12 cells.

    Science.gov (United States)

    Muñoz, F; Martín, M E; Salinas, M; Fando, J L

    2001-03-09

    We have investigated the effect of the mitochondrial uncoupler carbonyl cyanide p-trifluoromethoxyphenylhydrazone (FCCP) on protein synthesis rate and initiation factor 2 (eIF2) phosphorylation in PC12 cells differentiated with nerve growth factor. FCCP treatment induced a very rapid 2-fold increase in intracellular Ca(2+) concentration that was accompanied by a strong protein synthesis rate inhibition (68%). The translation inhibition correlated with an increased phosphorylation of the alpha subunit of eIF2 (eIF2 alpha) (25% vs. 7%, for FCCP-treated and control cells, respectively) and a 1.7-fold increase in the double-stranded RNA-dependent protein kinase activity. No changes in the PKR endoplasmic reticulum-related kinase or eIF2 alpha phosphatase were found. Translational regulation may play a significant role in the process triggered by mitochondrial calcium mobilization.

  12. Organometallics meet colloid chemistry: a case study in three phases based on molecular carbonyl precursors containing zinc and manganese.

    Science.gov (United States)

    Orlov, A; Roy, A; Lehmann, M; Driess, M; Polarz, S

    2007-01-17

    Two organometallic compounds containing zinc and manganese in different ratios are used as single-source precursors for the preparation of various new, bimetallic oxide materials with nanoscaled dimensions. It is shown that the materials synthesis can be performed in the solid-state, the liquid-phase, and even in the gas-phase. The molecular composition of the precursors determines the composition of the resulting materials. In addition, two novel methods for the preparation of highly crystalline metal oxide colloids are presented: The coupling between a gas-phase process and a colloidal approach, and the application of ozone as an oxidant for the transformation of metal carbonyls into oxides in the liquid phase.

  13. Increase of gluthatione S-transferase, carboxyl esterase and carbonyl reductase in Fasciola hepatica recovered from triclabendazole treated sheep.

    Science.gov (United States)

    Scarcella, S; Solana, M V; Fernandez, V; Lamenza, P; Ceballos, L; Solana, H

    2013-10-01

    Fasciolasis is a zoonotic parasitic disease caused by Fasciola hepatica and its control is mainly based on the use of triclabendazole (TCBZ). Parasite resistance to different anthelmintics is growing worldwide, including the resistance of F. hepatica to TCBZ. In the present work we evaluate "in vivo" the activity of xenobiotic metabolizing enzymes of phase I (carboxyl esterases) and phase II (glutathione S-transferases and carbonyl reductases) recovered of flukes from sheep treated with TCBZ. All three enzymes showed increased activity in TCBZ flukes returning 60h post-treatment at similar to baseline unexposed flukes. TCBZ action may induce secondary oxidative stress, which may explain the observed increment in activities of the analyzed enzymes as a defensive mechanism. The enzymes analyzed are candidates to participate actively in the development of resistance at TCBZ in F. hepatica.

  14. A NMR experiment for simultaneous correlations of valine and leucine/isoleucine methyls with carbonyl chemical shifts in proteins.

    Science.gov (United States)

    Tugarinov, Vitali; Venditti, Vincenzo; Marius Clore, G

    2014-01-01

    A methyl-detected 'out-and-back' NMR experiment for obtaining simultaneous correlations of methyl resonances of valine and isoleucine/leucine residues with backbone carbonyl chemical shifts, SIM-HMCM(CGCBCA)CO, is described. The developed pulse-scheme serves the purpose of convenience in recording a single data set for all Ile(δ1), Leu(δ) and Val(γ) (ILV) methyl positions instead of acquiring two separate spectra selective for valine or leucine/isoleucine residues. The SIM-HMCM(CGCBCA)CO experiment can be used for ILV methyl assignments in moderately sized protein systems (up to ~100 kDa) where the backbone chemical shifts of (13)C(α), (13)Cβ and (13)CO are known from prior NMR studies and where some losses in sensitivity can be tolerated for the sake of an overall reduction in NMR acquisition time.

  15. Aldo-keto reductase family 1 B10 protein detoxifies dietary and lipid-derived alpha, beta-unsaturated carbonyls at physiological levels

    Energy Technology Data Exchange (ETDEWEB)

    Zhong, Linlin [Department of Medical Microbiology, Immunology, and Cell Biology, SimmonsCooper Cancer Institute, Southern Illinois University School of Medicine, 913 N. Rutledge Street, Springfield, IL 62794-9626 (United States); Department of Neurobiology and Anatomy, China Medical University, Shenyang 110001 (China); Liu, Ziwen [Department of Medical Microbiology, Immunology, and Cell Biology, SimmonsCooper Cancer Institute, Southern Illinois University School of Medicine, 913 N. Rutledge Street, Springfield, IL 62794-9626 (United States); Department of Surgery, Peking Union Medical College Hospital, Beijing 100730 (China); Yan, Ruilan [Department of Medical Microbiology, Immunology, and Cell Biology, SimmonsCooper Cancer Institute, Southern Illinois University School of Medicine, 913 N. Rutledge Street, Springfield, IL 62794-9626 (United States); Johnson, Stephen [Carbon Dynamics Institute, LLC, 2835 via Verde Drive, Springfield, IL 62703-4325 (United States); Zhao, Yupei [Department of Surgery, Peking Union Medical College Hospital, Beijing 100730 (China); Fang, Xiubin [Department of Neurobiology and Anatomy, China Medical University, Shenyang 110001 (China); Cao, Deliang, E-mail: dcao@siumed.edu [Department of Medical Microbiology, Immunology, and Cell Biology, SimmonsCooper Cancer Institute, Southern Illinois University School of Medicine, 913 N. Rutledge Street, Springfield, IL 62794-9626 (United States)

    2009-09-18

    Alpha, beta-unsaturated carbonyls are highly reactive mutagens and carcinogens to which humans are exposed on a daily basis. This study demonstrates that aldo-keto reductase family 1 member B10 (AKR1B10) is a critical protein in detoxifying dietary and lipid-derived unsaturated carbonyls. Purified AKR1B10 recombinant protein efficiently catalyzed the reduction to less toxic alcohol forms of crotonaldehyde at 0.90 {mu}M, 4-hydroxynonenal (HNE) at 0.10 {mu}M, trans-2-hexanal at 0.10 {mu}M, and trans-2,4-hexadienal at 0.05 {mu}M, the concentrations at or lower than physiological exposures. Ectopically expressed AKR1B10 in 293T cells eliminated immediately HNE at 1 (subtoxic) or 5 {mu}M (toxic) by converting to 1,4-dihydroxynonene, protecting the cells from HNE toxicity. AKR1B10 protein also showed strong enzymatic activity toward glutathione-conjugated carbonyls. Taken together, our study results suggest that AKR1B10 specifically expressed in the intestine is physiologically important in protecting the host cell against dietary and lipid-derived cytotoxic carbonyls.

  16. Dormancy removal of apple seeds by cold stratification is associated with fluctuation in H2O2, NO production and protein carbonylation level.

    Science.gov (United States)

    Dębska, Karolina; Krasuska, Urszula; Budnicka, Katarzyna; Bogatek, Renata; Gniazdowska, Agnieszka

    2013-03-15

    Reactive oxygen (ROS) and nitrogen (RNS) species play a signaling role in seed dormancy alleviation and germination. Their action may be described by the oxidative/nitrosative "window/door". ROS accumulation in embryos could lead to oxidative modification of protein through carbonylation. Mature apple (Malus domestica Borkh.) seeds are dormant and do not germinate. Their dormancy may be overcome by 70-90 days long cold stratification. The aim of this work was to analyze the relationship between germinability of embryos isolated from cold (5°C) or warm (25°C) stratified apple seeds and ROS or nitric oxide (NO) production and accumulation of protein carbonyl groups. A biphasic pattern of variation in H2O2 concentration in the embryos during cold stratification was detected. H2O2 content increased markedly after 7 days of seeds imbibition at 5°C. After an additional two months of cold stratification, the H2O2 concentration in embryos reached the maximum. NO production by the embryos was low during entire period of stratification, but increased significantly in germination sensu stricto (i.e. phase II of the germination process). The highest content of protein carbonyl groups was detected after 6 weeks of cold stratification treatment. Fluctuation of H2O2 and protein carbonylation seems to play a pivotal role in seed dormancy alleviation by cold stratification, while NO appears to be necessary for seed germination.

  17. Research on compatibility of carbonylated piperylene petroleum resin and SBS%羰基化间戊二烯石油树脂与SBS相容性研究

    Institute of Scientific and Technical Information of China (English)

    毛兵; 张春梅; 李亮; 柳彩霞; 潘广勤

    2012-01-01

    The compatibility of carbonylated piperylene petroleum resin and SBS was investigated by analysis of glass-transition temperature of blend systems.The results showed that piperylene petroleum resin and hard block PS phase of SBS are incompatible.but the polarity of resin was improved after carbonylation,and the compatibility of resin and hard block PS phase was improved as well.The carbonylation time of resin is about 90 min,and the content of carbonylated resin in petroleum resin/SBS blends is more than 20%.The blends formed a homogeneous continuous phase,and they are completely compatible.%通过对共混体系玻璃化转变温度(Tg)的分析,研究了羰基化间戊二烯石油树脂与SBS的相容性.结果表明,间戊二烯石油树脂与SBS中的硬段PS不相容,经过羰基化处理后的树脂极性提高,相容性得到改善.羰基化处理时间为90min左右,羰基化石油树脂在共混体系中质量分数为20%以上,共混体系形成了均匀的连续相,2者完全相容.

  18. INHALATIONAL EXPOSURE TO CARBONYL SULFIDE (COS) PRODUCES BRAIN LESIONS AND ALTERED BRAINSTEM AUDITORY (BAER) AND SOMATOSENSORY (SEP) EVOKED POTENTIALS IN FISHCER 344N RATS.

    Science.gov (United States)

    Because of the amount of carbonyl sulfide (COS) emissions and the lack of toxicological data, COS was listed in the Clean Air Act of 1990 as a Hazardous Air Pollutant. In 1999 COS was nominated by the US EPA to the National Toxicology Program for additional toxicological investig...

  19. 12 WEEK EXPOSURE TO CARBONYL SULFIDE PRODUCES BRAIN LESIONS AND CHANGES IN BRAINSTEM AUDITORY (BAER) AND SOMATOSENAORY (SEP) EVOKED POTENTIALS IN FISCHER 344N RATS

    Science.gov (United States)

    Carbonyl sulfide (COS) is a chemical intermediate in the production of pesticides and herbicides, is a metabolite of carbon disulfide, is produced by the combustion of organic material, and is found occurring in nature. COS was included in a Toxic Substances Control Act request f...

  20. Ambient levels and temporal trends of VOCs, including carbonyl compounds, and ozone at Cabañeros National Park border, Spain

    Science.gov (United States)

    Villanueva, Florentina; Tapia, Araceli; Notario, Alberto; Albaladejo, José; Martínez, Ernesto

    2014-03-01

    Concentration levels of 15 carbonyls, 17 VOCs and ozone were studied at Cabañeros National Park border, Spain, in an area mainly constituted by holm oaks (Quercus ilex) and cork oaks (Quercus suber), along with scrubland formations such as rock-rose and heather. The compounds were collected by means of diffusive samplers from August-November 2010 and February-August 2011. Carbonyl compounds, VOCs and O3 were analysed by HPLC with diode array UV-Vis detector, GC-FID and by UV-visible spectrophotometry, respectively. The most abundant carbonyls were hexanal, acetone-acrolein, formaldehyde and acetaldehyde. Seasonal variation was apparent with maximum values observed in summer months. Total carbonyl concentrations ranged from 2.8 to 19.7 μg m-3. Most VOCs studied (using chemically desorbable cartridges) were either not detected or were below their detection limits, however, a parallel sampling using thermally desorbable cartridges, from May 22 to June 19, revealed the presence of much more VOCs, identified using GC-MS. O3 concentration ranged from 27.2 to 90.5 μg m-3, reaching the maximum monthly mean concentration in March (84.4 μg m-3). The analysis of back trajectories indicates the transport of polluted air masses from remote areas, mainly from the Mediterranean basin that should contribute to the high levels of ozone observed.

  1. Quantification of Carbonyl Compounds Generated from Ozone-Based Food Colorants Decomposition Using On-Fiber Derivatization-SPME-GC-MS

    Directory of Open Access Journals (Sweden)

    Wenda Zhu

    2014-12-01

    Full Text Available Fruit leathers (FLs production produces some not-to-specification material, which contains valuable ingredients like fruit pulp, sugars and acidulates. Recovery of FL for product recycling requires decolorization. In earlier research, we proved the efficiency of an ozone-based decolorization process; however, it produces carbonyls as major byproducts, which could be of concern. A headspace solid-phase microextraction with on-fiber derivatization followed by gas chromatography-mass spectrometry was developed for 10 carbonyls analysis in ozonated FL solution/suspension. Effects of dopant concentration, derivatization temperature and time were studied. The adapted method was used to analyze ozonated FL solution/suspension samples. Dopant concentration and derivatization temperature were optimized to 17 mg/mL and 60 °C, respectively. Competitive extraction was studied, and 5 s extraction time was used to avoid non-linear derivatization of 2-furfural. The detection limits (LODs for target carbonyls ranged from 0.016 and 0.030 µg/L. A much lower LOD (0.016 ppb for 2-furfural was achieved compared with 6 and 35 ppb in previous studies. Analysis results confirmed the robustness of the adapted method for quantification of carbonyls in recycled process water treated with ozone-based decolorization. Ethanal, hexanal, 2-furfural, and benzaldehyde were identified as byproducts of known toxicity but all found below levels for concern.

  2. Carbonylation and Loss-of-Function Analyses of SBPase Reveal Its Metabolic Interface Role in Oxidative Stress, Carbon Assimilation, and Multiple Aspects of Growth and Development in Arabidopsis

    Institute of Scientific and Technical Information of China (English)

    Xun-Liang Liu; Hai-Dong Yu; Yuan Guan; Ji-Kai Li; Fang-Qing Guo

    2012-01-01

    Sedoheptulose-1,7-bisphosphatase (SBPase) is a Calvin cycle enzyme and functions in photosynthetic carbon fixation.We found that SBPase was rapidly carbonylated in response to methyl viologen (MV) treatments in detached leaves of Arabidopsis plants.In vitro activity analysis of the purified recombinant SBPase showed that SBPase was carbonylated by hydroxyl radicals,which led to enzyme inactivation in an H2O2 dose-dependent manner.To determine the conformity with carbonylation-caused loss in enzymatic activity in response to stresses,we isolated a loss-of-function mutant sbp,which is deficient in SBPase-dependent carbon assimilation and starch biosynthesis,sbp mutant exhibited a severe growth retardation phenotype,especially for the developmental defects in leaves and flowers where SBPASE is highly expressed.The mutation of SBPASE caused growth retardation mainly through inhibition of cell division and expansion,which can be partially rescued by exogenous application of sucrose.Our findings demonstrate that ROS-induced oxidative damage to SBPase affects growth,development,and chloroplast biogenesis in Arabidopsis through inhibiting carbon assimilation efficiency.The data presented here provide a case study that such inactivation of SBPase caused by carbonyl modification may be a kind of adaptation for plants to restrict the operation of the reductive pentose phosphate pathway under stress conditions.

  3. Photocatalytic degradation of mixed gaseous carbonyl compounds at low level on adsorptive TiO2/SiO2 photocatalyst using a fluidized bed reactor.

    Science.gov (United States)

    Zhang, Maolin; An, Taicheng; Fu, Jiamo; Sheng, Guoying; Wang, Xinming; Hu, Xiaohong; Ding, Xuejun

    2006-06-01

    An adsorptive silica-supported titania photocatalyst TiO(2)/SiO(2) was prepared by using nanosized titania (anatase) immobilized on silica gel by the sol-gel technique with the titanium tetra isopropoxide as the main raw material and acetic acid as the acid catalyst. Meanwhile the structure and properties of the TiO(2)/SiO(2) photocatalyst were studied by means of many modern analysis techniques such as TEM, XRD, and BET. Gas-solid heterogeneous photocatalytic decomposition of four carbonyl compounds mixture at low concentration levels over ultraviolet irradiated TiO(2)/SiO(2) photocatalyst were carried out with high degradation efficiencies in a coaxial triple-cylinder-type fluidized bed photocatalytic reactor, which provided efficient continuous contact of ultraviolet photons, silica-supported titania photocatalyst, and gaseous reactants. Experimental results showed that the photocatalyst had a high adsorption performance and a good photocatalytic activity for four carbonyl compounds mixture. Some factors influencing the photocatalytic decomposition of the mixed carbonyl compounds, i.e. the gas flowrate, relative humidity, concentration of oxygen, and illumination time, were discussed in detail. It is found that the photocatalytic reaction rate of four carbonyl compounds decreased in this order: propionaldehyde, acetone, acetaldehyde and formaldehyde.

  4. Lewis Base-Catalyzed Formation of α-Trifluoromethyl Alcohol from CF3SiMe3 and Carbonyl-Containing Compounds

    Institute of Scientific and Technical Information of China (English)

    ZHU Shi-Fa; PANG Wan; XING Chun-Hui; ZHU Shi-Zheng

    2007-01-01

    Lewis base could catalyze the formation of α-trifluoromethyl alcohol from CF3SiMe3 and carbonyl-containingcompounds. It was found that the a-trilluoromethyl alcohol could also be used to promote the synthesis in basic conditions.

  5. Design, synthesis, and evaluation of carnosine derivatives as selective and efficient sequestering agents of cytotoxic reactive carbonyl species.

    Science.gov (United States)

    Vistoli, Giulio; Orioli, Marica; Pedretti, Alessandro; Regazzoni, Luca; Canevotti, Renato; Negrisoli, Gianpaolo; Carini, Marina; Aldini, Giancarlo

    2009-06-01

    Carnosine aryl derivatives as sequestering agents of RCS: Reactive carbonyl species (RCS) are cytotoxic mediators representing a novel drug target, as they are presumed to play a pathogenic role in several diseases. Carnosine is a selective RCS-sequestering agent, but is rapidly hydrolyzed by serum carnosinase. Herein we describe the in silico design, synthesis, and evaluation of a set of carnosine aryl derivatives.Reactive carbonyl species (RCS) are important cytotoxic mediators generated by lipid oxidation of polyunsaturated fatty acids (PUFAs) and represent a novel drug target, as they are presumed to play a pathogenic role in several diseases. L-Carnosine (L-CAR, beta-alanyl-L-histidine) is a specific detoxifying agent of RCS, but is rapidly hydrolyzed in human serum by carnosinase, a specific dipeptidase. Herein we describe the in silico design, synthesis, and biological evaluation of carnosine derivatives that are resistant to carnosinase and that have increased quenching efficacy. Stability against carnosinase-mediated turnover was achieved by isomerization of the histidine residue, leading to D-carnosine (D-CAR, beta-alanyl-D-histidine), which maintains the same quenching activity of L-carnosine. A molecular modeling approach was then used to design derivatives characterized by an increased quenching efficacy. The most promising candidates were synthesized, and their stability and quenching activity were evaluated. This study describes a set of aryl derivatives that are characterized by high stability in human plasma and a quenching activity toward 4-hydroxy-trans-2-nonenal (HNE), chosen as a model of RCS, up to threefold greater than D-carnosine.

  6. Intermediates relevant to the carbonylation of manganese alkyl complexes interrogated by time resolved infrared and optical spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Boese, W.T.; Ford, P.C. [Univ. of California, Santa Barbara, CA (United States)

    1995-08-16

    Intermediates relevant to the carbonylation of metal alkyl complexes have been generated by laser flash photolysis of the manganese acyl complexes RC(O)Mn(CO){sub 5} (R = CH{sub 3}, CD{sub 3}, CH{sub 2}CH{sub 3}, CH{sub 2}F, CF{sub 3}). This results in immediate CO photodissociation to give intermediate acyl complexes which were observed by time resolved infrared (TRIR) and time resolved optical (TRO) spectroscopy. In the presence of added ligands, such intermediates are trapped to form stable cis-substituted octahedral complexes in competition with alkyl migration from the acyl group to give the alkyl pentacarbonyl complexes RMn(CO){sub 5}. The spectra and reactivity of the intermediate (I) derived from CH{sub 3}C(O)Mn(CO){sub 5} (A) indicate that this exists as the chelated acyl complex ({eta}{sup 2}-CH{sub 3}CO)Mn(CO){sub 4} in weakly coordinating solvents such as cyclohexane but as the solvento species cis-CH{sub 3}C(O)Mn(CO){sub 4}(THF) in tetrahydrofuran. Comparisons with thermal reaction kinetics support the assertion that the intermediates generated photochemically are indeed relevant to understanding the mechanism for CH{sub 3}Mn(CO){sub 5} carbonylation. The CF{sub 3} and CH{sub 2}F analogs of I are much more reactive than I in cyclohexane solution, and this has been interpreted in terms of the {eta}{sup 2}-acyl configuration being destabilized by these electron-withdrawing groups. 33 refs., 10 figs., 4 tabs.

  7. Metal carbonyl-hydrosilane reactions and hydrosilation catalysis. Final report for period May 1, 1995 - August 14, 1999

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, Alan R.

    2001-04-14

    Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a doxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(CO){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(l) precatalysts. The reaction chemistry of the above and other Mn alkyl complexes with hydrosilanes was studied in order to probe catalysis mechanism(s). Thus, Mn(CO){sub 5} methyl, benzyl, acetyl, and benzoyl (4 p-substituents) complexes reacted with hydrosilines by four different mechanisms, which were established. A noteworthy development was that the methyl and benzoyl complexes gave moderate yields of a new ({eta}{sup 2}-Si-H) silane adduct (CO){sub 4}Mn(SiMe{sub 2}Ph)(H-SiMe{sub 2}Ph), which is stable in the presence of excess silane. This silane adduct promotes all three catalytic reactions; its extraordinary activity and potential selectivity are under study.

  8. Different Response of Carbonyl Carotenoids to Solvent Proticity Helps To Estimate Structure of the Unknown Carotenoid from Chromera velia.

    Science.gov (United States)

    Keşan, Gürkan; Durchan, Milan; Tichý, Josef; Minofar, Babak; Kuznetsova, Valentyna; Fuciman, Marcel; Šlouf, Václav; Parlak, Cemal; Polívka, Tomáš

    2015-10-01

    In order to estimate the possible structure of the unknown carbonyl carotenoid related to isofucoxanthin from Chromera velia denoted as isofucoxanthin-like carotenoid (Ifx-l), we employed steady-state and ultrafast time-resolved spectroscopic techniques to investigate spectroscopic properties of Ifx-l in various solvents. The results were compared with those measured for related carotenoids with known structure: fucoxanthin (Fx) and isofucoxanthin (Ifx). The experimental data were complemented by quantum chemistry calculations and molecular modeling. The data show that Ifx-l must have longer effective conjugation length than Ifx. Yet, the magnitude of polarity-dependent changes in Ifx-l is larger than for Ifx, suggesting significant differences in structure of these two carotenoids. The most interesting spectroscopic feature of Ifx-l is its response to solvent proticity. The transient absorption data show that (1) the magnitude of the ICT-like band of Ifx-l in acetonitrile is larger than in methanol and (2) the S1/ICT lifetime of Ifx-l in acetonitrile, 4 ps, is markedly shorter than in methanol (10 ps). This is opposite behavior than for Fx and Ifx whose S1/ICT lifetimes are always shorter in protic solvent methanol (20 and 13 ps) than in aprotic acetonitrile (30 and 17 ps). Comparison with other carbonyl carotenoids reported earlier showed that proticity response of Ifx-l is consistent with presence of a conjugated lactone ring. Combining the experimental data and quantum chemistry calculations, we estimated a possible structure of Ifx-l.

  9. Highly efficient energy transfer from a carbonyl carotenoid to chlorophyll a in the main light harvesting complex of Chromera velia.

    Science.gov (United States)

    Durchan, Milan; Keşan, Gürkan; Slouf, Václav; Fuciman, Marcel; Staleva, Hristina; Tichý, Josef; Litvín, Radek; Bína, David; Vácha, František; Polívka, Tomáš

    2014-10-01

    We report on energy transfer pathways in the main light-harvesting complex of photosynthetic relative of apicomplexan parasites, Chromera velia. This complex, denoted CLH, belongs to the family of FCP proteins and contains chlorophyll (Chl) a, violaxanthin, and the so far unidentified carbonyl carotenoid related to isofucoxanthin. The overall carotenoid-to-Chl-a energy transfer exhibits efficiency over 90% which is the largest among the FCP-like proteins studied so far. Three spectroscopically different isofucoxanthin-like molecules were identified in CLH, each having slightly different energy transfer efficiency that increases from isofucoxanthin-like molecules absorbing in the blue part of the spectrum to those absorbing in the reddest part of spectrum. Part of the energy transfer from carotenoids proceeds via the ultrafast S2 channel of both the violaxanthin and isofucoxanthin-like carotenoid, but major energy transfer pathway proceeds via the S1/ICT state of the isofucoxanthin-like carotenoid. Two S1/ICT-mediated channels characterized by time constants of ~0.5 and ~4ps were found. For the isofucoxanthin-like carotenoid excited at 480nm the slower channel dominates, while those excited at 540nm employs predominantly the fast 0.5ps channel. Comparing these data with the excited-state properties of the isofucoxanthin-like carotenoid in solution we conclude that, contrary to other members of the FCP family employing carbonyl carotenoids, CLH complex suppresses the charge transfer character of the S1/ICT state of the isofucoxanthin-like carotenoid to achieve the high carotenoid-to-Chl-a energy transfer efficiency.

  10. Overcoming uncertainty with carbonyl sulfide-based GPP estimates: observing and modeling soil COS fluxes in terrestrial ecosystems

    Science.gov (United States)

    Whelan, M.; Hilton, T. W.; Berry, J. A.; Berkelhammer, M. B.; Desai, A. R.; Rastogi, B.; Campbell, J. E.

    2015-12-01

    Significant carbonyl sulfide (COS) exchange by soils limits the applicability of net ecosystem COS flux observations as a proxy for stomatal trace gas exchange. High frequency measurements of COS over urban and natural ecosystems offer a potential window into processes regulating the carbon and water cycle: photosynthetic carbon uptake and stomatal conductance. COS diffuses through plant stomata and is irreversibly consumed by enzymes involved in photosynthesis. In certain environments, the magnitude of soil COS fluxes may constitute one-quarter of COS uptake by plants. Here we present a way of anticipating conditions when anomalously large soil COS fluxes are likely to occur and be taken into account. Previous studies have pointed to either a tendency for soil uptake of COS from the atmosphere with a soil moisture optimum, or exponential COS production coincident with temperature. Data from field and laboratory studies were used to deconvolve the two processes. CO2 and COS fluxes were observed from forest, desert, grassland, and agricultural soils under a range of temperature and soil moisture conditions. We demonstrate how to estimate temperature and soil moisture impacts on COS soil production based on our cross-site incubations. By building a model of soil COS exchange that combines production and consumption terms, we offer a framework for interpreting the two disparate conclusions about soil COS exchange in previous studies. Such a construction should be used in ecosystem and continental scale modeling of COS fluxes to anticipate where the influence of soil COS exchange needs to be accounted for, resulting in greater utility of carbonyl sulfide as a tracer of plant physiological processes.

  11. Analysis of Selected Carbonyl Compounds in Tobacco Samples by Using Pentafluorobenzylhydroxylamine Derivatization and Gas Chromatography-Mass Spectrometry

    Directory of Open Access Journals (Sweden)

    Bao Mingliang

    2014-09-01

    Full Text Available Nous avons mis au point une méthode, à la fois fiable, précise et simple, d’analyse courante des composés carbonylés, en ce compris le formaldéhyde, l’acétaldéhyde, l’acétone, le propionaldéhyde, la méthyléthylcétone (MEC, le butyraldéhyde et le crotonaldéhyde, présents à l’état de traces dans les produits de tabac ouvré. Un échantillon d’un gramme de tabac, additionné d’un mélange de carbonyles marqués d’un isotope en guise de normes internes, a été extrait par l’eau. Une part de l’extrait aqueux a subi un processus de dérivatisation à l’aide de chlorhydrate d’o-(2,3,4,5,6-pentafluorobenzyle-hydroxylamine (PFBHA. Les dérivés carbonylés obtenus à l’aide du PFBHA ont ensuite été extraits par l’hexane et analysés par chromatographie en phase gazeuse couplée à la spectrométrie de masse (GC-MS. La précision et l’exactitude de la méthode ont été évaluées au regard d’une cigarette de référence Kentucky « additionnée » 3R4F et de produits de référence sans fumée CORESTA CRP1, CRP2, CRP3 et CRP4. Eu égard aux composés carbonylés analysés, d’excellents taux de précision (5-10% et de récupération (95-107% ont été observés avec divers produits du tabac « additionnés », à l’exception de l’acroléine, qui s’est avérée instable dans tous les produits du tabac testés. L’intervalle linéaire de la méthode mise au point s’est étendu de 0,07 à 36 μg/g avec des limites de quantification variant de 0,10 à 0,15 μg/g. Grâce à la présente méthode, le formaldéhyde (0,31-6,24 μg/g et l’acétaldéhyde (0,84- 17,7 μg/g ont été décelés dans tous les produits de référence testés. L’acétone (0,55-2,12 μg/g a été trouvée dans les produits 3R4F, CRP1, CRP2 et CRP3. Des niveaux décelables de propionaldéhyde n’ont été observés que dans les produits CRP1 et CRP3. Les niveaux de MEC, butyraldéhyde et crotonaldéhyde décelés dans tous

  12. Ambient Levels of Carbonyl Compounds in Shanghai,China%上海市大气羰基化合物水平研究

    Institute of Scientific and Technical Information of China (English)

    黄娟; 冯艳丽; 熊斌; 傅家谟; 盛国英

    2009-01-01

    建立乙腈-水-四氢呋喃三元梯度洗脱方法,利用HPLC-UV分离定量22种羰基化合物,并成功地分离了丙酮和丙烯醛.选取了2个采样点(工业区和商业区)对上海市大气中的羰基化合物进行了研究.结果表明,甲醛、乙醛、丙酮和2-丁酮(C1-C4羰基化合物)是上海市大气浓度较高的化合物,它们分别占羰基化合物总量的78.95%(工业区)和77.63%(商业区).在工业区,甲醛、乙醛、丙酮和2-丁酮的平均浓度分别为10.36、15.32、9.95和4.56 μg/m~3;在商业区,它们的平均浓度分别为10.00、10.04、7.80和2.81μg/m~3.工业区的C1-C4羰基化合物平均水平要高于商业区.羰基化合物总量亦是工业区(53.64μg/m~3)高于商业区(41.96μg/m~3).羰基化合物的昼夜变化在工业区和商业区也比较一致,均是早高峰和晚上这2个时段的浓度很高,而其它时段较低.%A ternary-mobile phase program with acetonitrile, water and tetrahydrofuran was developed to identify and quantify 22 carbonyl compounds species by HPLC-UV. The analytical method succeeded in separating acrolein from acetone. Two sampling sites (industrial district and business district) were chosen to study carbonyl compounds levels in ambient air of Shanghai. The results indicated that formaldehyde, acetaldehyde, acetone and 2-butanone (C1-C4 carbonyl compounds) were the most abundant carbonyl compounds in ambient air of Shanghai. The four carbonyls together accounted for 78.95% (industrial district) and 77.63% (business district) of the total carbonyl compounds, respectively. In industrial district, the mean concentrations of formaldehyde, acetaldehyde, acetone and 2-butanone were 10.36, 15.32, 9.95 and 4.56 μg/m~3, respectively; in business district, their mean levels were 10.00, 10.04, 7.80 and 2.81 μg/m~3, respectively. So the mean levels of C1-C4 carbonyl compounds in industrial district were higher than in business district. The higher concentrations of the total

  13. Axial ligand effects on vibrational dynamics of iron in heme carbonyl studied by nuclear resonance vibrational spectroscopy.

    Science.gov (United States)

    Ohta, Takehiro; Liu, Jin-Gang; Saito, Makina; Kobayashi, Yasuhiro; Yoda, Yoshitaka; Seto, Makoto; Naruta, Yoshinori

    2012-11-29

    Nuclear resonance vibrational spectroscopy (NRVS) and density functional theory calculation (DFT) have been applied to illuminate the effect of axial ligation on the vibrational dynamics of iron in heme carbonyl. The analyses of the NRVS data of five- (5c) and six-coordinate (6c) heme-CO complexes indicate that the prominent feature of (57)Fe partial vibrational density of state ((57)FePVDOS) at the 250-300 cm(-1) region is significantly affected by the association of the axial ligand. The DFT calculations predict that the prominent (57)FePVDOS is composed of iron in-plane motions which are coupled with porphyrin pyrrole in-plane (ν(49), ν(50), and ν(53)), an out-of-plane (γ(8)) (two of four pyrrole rings include the in-plane modes, while the rest of pyrrole rings vibrate along the out-of-plane coordinate), and out-of-phase carbonyl C and O atom displacement perpendicular to the Fe-C-O axis. Thus, in the case of the 5c CO-heme the prominent (57)FePVDOS shows sharp and intense feature because of the degeneracy of the e symmetry mode within the framework of C(4v) symmetry molecule, whereas the association of the axial imidazole ligand in the 6c complex with the lowered symmetry results in split of the degenerate vibrational energy as indicated by broader and lower intensity features of the corresponding NRVS peak compared to the 5c structure. The vibrational energy of the iron in-plane motion in the 6c complex is higher than that in 5c, implying that the iron in the 6c complex includes stronger in-plane interaction with the porphyrin compared to 5c. The iron in-plane mode above 500 cm(-1), which is predominantly coupled with the out-of-phase carbonyl C and O atom motion perpendicular to Fe-C-O, called as Fe-C-O bending mode (δ(Fe-C-O)), also suggests that the 6c structure involves a larger force constant for the e symmetry mode than 5c. The DFT calculations along with the NRVS data suggest that the stiffened iron in-plane motion in the 6c complex can be ascribed

  14. Origins of n-alkanes, carbonyl compounds and molecular biomarkers in atmospheric fine and coarse particles of Athens, Greece.

    Science.gov (United States)

    Andreou, G; Rapsomanikis, S

    2009-10-15

    The abundance and origin of aliphatic hydrocarbons, carbonyl compounds and molecular biomarkers found in the aliphatic fraction of PM(10-2.5) and PM(2.5) in the centre of Athens Greece are discussed in an attempt to reveal seasonal air pollution characteristics of the conurbation. Each extract was fractionated into individual compound classes and was analyzed using gas chromatography coupled to mass spectrometry. Normal alkanes, ranging from C(14) to C(35), were abundant in PM(10-2.5) and PM(2.5) samples during both sampling campaigns. The daily concentration of total n-alkanes was up to 438 ng m(-3) for PM(10-2.5) and up to 511 ng m(-3) for PM(2.5). Additionally, gaseous concentrations of n-alkanes were calculated, revealing that the relative proportions between gaseous and particle phases of individual compounds may differ significantly between summer and late winter. Normal alkanals and alkan-2-ones were only detected in the fine fraction of particulate matter and their concentrations were much lower than the n-alkane concentrations. Several geochemical parameters were used to qualitatively reconcile the sources of organic aerosol. The carbon preference index (CPI) of the coarse particles in August had the highest value, while in March the leaf wax contribution decreased significantly and the CPI value was very close to unity for both sites. Maximum concentrations of carbonyl compounds were reported in the range of C(15)-C(20), demonstrating that they were formed from anthropogenic activity or from atmospheric oxidative processes. 6, 10, 14-trimethylpentadecan-2-one, a marker of biogenic input, was also detected in our samples. Molecular biomarker compounds confirmed that ca. 60% of the aliphatic fraction on the sampled atmospheric particles originated from petroleum and not from any contemporary biogenic sources. Pristane and phytane were detected in the fine fraction with their presence indicating sources of fossil fuel in the range of C(16)-C(20). At all

  15. Efficicent (R-phenylethanol production with enantioselectivity-alerted (S-carbonyl reductase II and NADPH regeneration.

    Directory of Open Access Journals (Sweden)

    Rongzhen Zhang

    Full Text Available The NADPH-dependent (S-carbonyl reductaseII from Candida parapsilosis catalyzes acetophenone to chiral phenylethanol in a very low yield of 3.2%. Site-directed mutagenesis was used to design two mutants Ala220Asp and Glu228Ser, inside or adjacent to the substrate-binding pocket. Both mutations caused a significant enantioselectivity shift toward (R-phenylethanol in the reduction of acetophenone. The variant E228S produced (R-phenylethanol with an optical purity above 99%, in 80.2% yield. The E228S mutation resulted in a 4.6-fold decrease in the K M value, but nearly 5-fold and 21-fold increases in the k cat and k cat/K M values with respect to the wild type. For NADPH regeneration, Bacillus sp. YX-1 glucose dehydrogenase was introduced into the (R-phenylethanol pathway. A coexpression system containing E228S and glucose dehydrogenase was constructed. The system was optimized by altering the coding gene order on the plasmid and using the Shine-Dalgarno sequence and the aligned spacing sequence as a linker between them. The presence of glucose dehydrogenase increased the NADPH concentration slightly and decreased NADP(+ pool 2- to 4-fold; the NADPH/NADP(+ ratio was improved 2- to 5-fold. The recombinant Escherichia coli/pET-MS-SD-AS-G, with E228S located upstream and glucose dehydrogenase downstream, showed excellent performance, giving (R-phenylethanol of an optical purity of 99.5 % in 92.2% yield in 12 h in the absence of an external cofactor. When 0.06 mM NADP(+ was added at the beginning of the reaction, the reaction duration was reduced to 1 h. Optimization of the coexpression system stimulated an over 30-fold increase in the yield of (R-phenylethanol, and simultaneously reduced the reaction time 48-fold compared with the wild-type enzyme. This report describes possible mechanisms for alteration of the enantiopreferences of carbonyl reductases by site mutation, and cofactor rebalancing pathways for efficient chiral alcohols production.

  16. Reductive Umpolung of Carbonyl Derivatives with Visible-Light Photoredox Catalysis: Direct Access to Vicinal Diamines and Amino Alcohols via α-Amino Radicals and Ketyl Radicals

    KAUST Repository

    Fava, Eleonora

    2016-05-02

    Visible-light-mediated photoredox-catalyzed aldimine-aniline and aldehyde-aniline couplings have been realized. The reductive single electron transfer (SET) umpolung of various carbonyl derivatives enabled the generation of intermediary ketyl and α-amino radical anions, which were utilized for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols. Anilines can be coupled with aldimines or aldehydes in a visible-light-mediated photoredox-catalyzed process. Reductive single electron transfer (SET) umpolung of the carbonyl derivatives leads to the generation of intermediary ketyl and α-amino radical anions, which were used for the synthesis of unsymmetrically substituted 1,2-diamines and amino alcohols.

  17. Iron-Carbonyl-Catalyzed Redox-Neutral [4+2] Annulation of N-H Imines and Internal Alkynes by C-H Bond Activation.

    Science.gov (United States)

    Jia, Teng; Zhao, Chongyang; He, Ruoyu; Chen, Hui; Wang, Congyang

    2016-04-18

    Stoichiometric C-H bond activation of arenes mediated by iron carbonyls was reported by Pauson as early as in 1965, yet the catalytic C-H transformations have not been developed. Herein, an iron-catalyzed annulation of N-H imines and internal alkynes to furnish cis-3,4-dihydroisoquinolines is described, and represents the first iron-carbonyl-catalyzed C-H activation reaction of arenes. Remarkablely, this is also the first redox-neutral [4+2] annulation of imines and alkynes proceeding by C-H activation. The reaction also features only cis stereoselectivity and excellent atom economy as neither base, nor external ligand, nor additive is required. Experimental and theoretical studies reveal an oxidative addition mechanism for C-H bond activation to afford a dinuclear ferracycle and a synergetic diiron-promoted H-transfer to the alkyne as the turnover-determining step.

  18. Visible-light-induced, Ir-catalyzed reactions of N-methyl-N-((trimethylsilylmethylaniline with cyclic α,β-unsaturated carbonyl compounds

    Directory of Open Access Journals (Sweden)

    Dominik Lenhart

    2014-04-01

    Full Text Available N-Methyl-N-((trimethylsilylmethylaniline was employed as reagent in visible-light-induced, iridium-catalyzed addition reactions to cyclic α,β-unsaturated carbonyl compounds. Typical reaction conditions included the use of one equivalent of the reaction substrate, 1.5 equivalents of the aniline and 2.5 mol % (in MeOH or 1.0 mol % (in CH2Cl2 [Ir(ppy2(dtbbpy]BF4 as the catalyst. Two major reaction products were obtained in combined yields of 30–67%. One product resulted from aminomethyl radical addition, the other product was a tricyclic compound, which is likely formed by attack of the intermediately formed α-carbonyl radical at the phenyl ring. For five-membered α,β-unsaturated lactone and lactam substrates, the latter products were the only products isolated. For the six-membered lactones and lactams and for cyclopentenone the simple addition products prevailed.

  19. Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand.

    Science.gov (United States)

    Shang, Rui; Ilies, Laurean; Nakamura, Eiichi

    2016-08-17

    Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.

  20. Antimycobacterial evaluation of novel [4,5-dihydro-1H-pyrazole-1-carbonyl]pyridine derivatives synthesized by microwave-mediated Michael addition.

    Science.gov (United States)

    Sedighi, Vida; Azerang, Parisa; Sardari, Soroush

    2015-06-01

    The focus of this study is the synthesis and biological activity evaluation of a series of dibenzalaceton derivatives (3a-3n) and novel [4,5-dihydro-1H-pyrazole-1-carbonyl]pyridine derivatives (5a-5g) against Mycobacterium bovis, Bacillus Calmette-Guerin (BCG). Dibenzalacetone derivatives were synthesized by benzaldehyde derivatives. The [4,5-dihydro-1H-pyrazole-1-carbonyl]pyridine derivatives were synthesized by Michael addition reaction and using green chemistry microwave-mediated method. All compounds were evaluated against BCG and the activity expressed as minimum inhibitory concentration (MIC) in μM. The result showed good activity for all the compounds especially compounds (3a), (3n), and (5a) illustrated high activity (7.03, 8.10 and 5.37 μM, respectively).

  1. Synthesis and structure-activity relationships of new carbonyl guanidine derivatives as novel dual 5-HT2B and 5-HT7 receptor antagonists.

    Science.gov (United States)

    Moritomo, Ayako; Yamada, Hiroyoshi; Watanabe, Toshihiro; Itahana, Hirotsune; Akuzawa, Shinobu; Okada, Minoru; Ohta, Mitsuaki

    2013-12-15

    To identify potent dual 5-HT2B and 5-HT7 receptor antagonists, we synthesized a series of novel carbonyl guanidine derivatives and examined their structure-activity relationships. Among these compounds, N-(9-hydroxy-9H-fluorene-2-carbonyl)guanidine (10) had a good in vitro profile, that is, potent affinity for human 5-HT2B and 5-HT7 receptor subtypes (Ki=1.8 nM and Ki=17.6 nM, respectively) and high selectivity over 5-HT2A, 5-HT2C, α1, D2 and M1 receptors. Compound 10 also showed a suppressing effect on 5-HT-induced dural protein extravasation in guinea pigs when orally administered.

  2. 植物对羰基化合物的排放与吸收研究进展%Carbonyl compounds emission and uptake by plant: Research progress

    Institute of Scientific and Technical Information of China (English)

    李剑; 蔡竟; 颜流水; 李羚娜; 陶敏

    2013-01-01

    综述了植物排放、吸收羰基化合物的研究成果,讨论了植物与大气之间羰基化合物的交换补偿点问题.气孔和角质层的吸收是醛类被植物净化的重要途径.羰基化合物进入植物叶片后,在叶片体内酶的作用下绝大部分被代谢为有机酸、糖类、氨基酸、二氧化碳等产物.根据补偿点及周围大气中羰基化合物的浓度可初步推断出植物与大气之间羰基化合物的交换方向.简要叙述了目前植物排放羰基化合物以及植物叶片中羰基化合物的分析方法,如DNPH/HPLC/UV和PFPH/GC/MS法.最后指出未来的研究热点为:改进和优化植物排放羰基化合物的分析方法和研究体系(如植物-土壤体系)、扩大植物排放羰基化合物的检测种类范围、筛选净化污染能力强的植物物种,以及推广植物修复大气污染技术.%This paper reviewed the researches on the carbonyl compounds emission and uptake by plants, and discussed the compensation point of the bidirectional exchange of carbonyl compounds between plants and atmosphere. The uptake by leaf stomata and stratum corneum is the principal way for the purification of air aldehydes by plants. After entering into plant leaves, most parts of carbonyl compounds can be metabolized into organic acid, glucide, amino acid, and carbon dioxide, etc. , by the endoenzymes in leaves. The exchange direction of the carbonyl compounds between plants and atmosphere can be preliminarily predicted by the compensation point and the concentrations of ambient carbonyl compounds. This paper summarized the analytical methods such as DNPH/HPLC/UV and PFPH/GC/MS used for the determination of carbonyl compounds emitted from plants or in plant leaves. The main research interests in the future were pointed out, e. g. , to improve and optimize the analytical methods for the determination of carbonyl compounds emitted from plants and the researches on systems (e. g. , plant-soil system), to

  3. Effects of organic contaminants in reactive oxygen species, protein carbonylation and DNA damage on digestive gland and haemolymph of land snails.

    Science.gov (United States)

    Itziou, A; Kaloyianni, M; Dimitriadis, V K

    2011-10-01

    The present study focused on early responses of land snails Eobania vermiculata to organic environmental contaminants, by investigating the use of a newly-established method for the measurement of protein carbonylation as a new biomarker of terrestrial pollution, as well as by measuring the ROS production and the DNA damage. Land snails were exposed to different concentrations of chlorpyrifos, parathion-methyl or PAHs in vivo or in vitro in the laboratory. The susceptibility of exposed snails was increased in relation to oxidative stress induced by contaminants tested. A statistically significant increase in ROS production, protein carbonylation and DNA damage was revealed in the snails treated with pollutants, compared to the untreated ones. The results indicated the effectiveness of measuring ROS production and DNA damage and reinforce the application of the present ELISA method in organic terrestrial pollution biomonitoring studies.

  4. Organic carbonyl compounds in Albuquerque, New Mexico, air: A preliminary study of the effects of oxygenated fuel use

    Energy Technology Data Exchange (ETDEWEB)

    Popp, C.J.; Zhang, Lin [New Mexico Inst. of Mining and Technology, Socorro, NM (United States). Dept. of Chemistry; Gaffney, J.S. [Argonne National Lab., IL (United States)

    1993-06-01

    A suite of inorganic and organic species were analyzed for four 2--4 day time periods over a year in Albuquerque, New Mexico to determine baseline conditions for organic pollutants under the current air pollution control parameters. Concentrations of low molecular weight carbonyl compounds were relatively high compared with areas such as Los Angeles. Formio acid concentrations in air samples were significant even in winter. In addition, ratios of peroxypropionyl nitrate to peroxyacyetyl nitrate are higher than expected and may be related to the use of oxygenated fuels which are used to mitigate CO concentrations. The number of CO violations in Albuquerque has decreased steadily since 1982 and the downward trend has continued since 1989 when oxygenated fuel use was mandated. It is, therefore, difficult to correlate the drop in CO violations directly to the use of oxygenated fuels when such factors as fleet turnover, woodburning controls, emissions testing and meteorological conditions also may be playing significant roles. More detailed studies are needed to determine the specific relationship between the use of oxygenated fuels and the air quality in Albuquerque, New Mexico and similar urban areas in the western United States.

  5. Enzymatic synthesis of an ezetimibe intermediate using carbonyl reductase coupled with glucose dehydrogenase in an aqueous-organic solvent system.

    Science.gov (United States)

    Liu, Zhi-Qiang; Dong, Si-Chuan; Yin, Huan-Huan; Xue, Ya-Ping; Tang, Xiao-Ling; Zhang, Xiao-Jian; He, Jun-Yao; Zheng, Yu-Guo

    2017-04-01

    (4S)-3-[(5S)-5-(4-Fluorophenyl)-5-hydroxypentanoyl]-4-phenyl-1,3-oxazolidin-2-one ((S)-ET-5) is an important chiral intermediate in the synthesis of chiral side chain of ezetimibe. Recombinant Escherichia coli expressing carbonyl reductase (CBR) was successfully constructed in this study. The total E. coli biomass and the specific activity of recombinant CBR in 5L fermenter culture were 10.9gDCWL(-1) and 14900.3Ug(-1)DCW, respectively. The dual-enzyme coupled biocatalytic process in an aqueous-organic biphasic solvent system was first constructed using p-xylene as the optimal organic phase under optimized reaction conditions, and 150gL(-1) (4S)-3-[5-(4-fluorophenyl)-1,5-dioxophentyl]-4-phenyl-1,3-oxazolidin-2-one (ET-4) was successfully converted to (S)-ET-5 with a conversion of 99.1% and diastereomeric excess of 99% after 24-h, which are the highest values reported to date for the production of (S)-ET-5.

  6. Enhancement effects of ultrasound assisted in the synthesis of NiAl hydrotalcite for carbonyl sulfide removal.

    Science.gov (United States)

    Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Gao, Fengyu; Yu, Qingjun; Zhou, Yuansong; Wang, Jiangen; Huang, Yonghai; Yang, Zhongyu

    2016-09-01

    Ultrasonic effect in the synthesis of catalysts of NiAl oxides prepared starting from the coprecipitation method of a hydrotalcite structure was evaluated in this work. Removal of carbonyl sulfide (COS) at low temperature over the hydrotalcite-derived oxides was studied. The samples were characterized by X-ray Diffraction (XRD), scanning electron microscope (SEM), N2 adsorption/desorption techniques, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and CO2 temperature-programmed desorption (TPD). It is found that hydrotalcite treated with ultrasonic has smaller average crystallite size and higher particle dispersion compared to hydrotalcite without ultrasonic treatment. As a result, mixed oxides derived from hydrotalcite treated with ultrasonic show more developed pore structure which is good for the physical adsorption of gaseous pollutant. The result of desulfuration test showed that removal efficiency of COS on the NiAl mixed oxides prepared by ultrasonic method (30min) is greater than that on the catalyst prepared without the ultrasonic irradiation assistance with the same aging time. One important reason for the high activity is that when the ultrasonic is used the number of weak basic sites (OH(-) groups) and moderate basic sites (M-O) was increased, whereas the number of strong basic sites (O(2-)) was decreased. Therefore, ultrasonic treatment promoted the COS hydrolysis and suppress the poisoning of the catalyst.

  7. Photoaddition reactions of silyl ketene acetals with aromatic carbonyl compounds: a new procedure for {beta}-hydroxyester synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Yoon, Ung Chan; Kim, Moon Jung; Moon, Jae Joon; Oh, Sun Wha; Kim, Hyun Jin [Pusan National Univ., Pusan (Korea, Republic of); Mariano, Patrick S. [University of New Mexico, Albuquerque (United States)

    2002-09-01

    Photochemical reactions of aromatic carbonyl compounds with silyl ketene acetals have been explored. Irradiation of acetonitrile or benzene solutions containing aryl aldehydes or ketones in the presence of silyl ketene acetals is observed to promote formation of {beta}-hydroxyester, 2,2-dioxyoxetane and 3,3-dioxyoxetane products. The ratios of these photoproducts, which arise by competitive single electron transfer (SET) and classical Paterno-Buchi mechanistic pathway, is found to be dependent on the degree of methyl-substitution on the vinyl moieties of the ketene acetals in a manner which reflects expected alkyl substituent effects on the oxidation potentials of these electron rich donors. An analysis of the product distribution arising by irradiation of a solution containing butyrophenone (6) and the silyl ketene acetal 9, derived from methyl isobutyrate, provides an estimate of the rate constants for the competitive Norrish type II, SET and Paterno-Buchi processes occurring. Finally, sequences involving silyl ketene acetal-aryl aldehyde or ketone photoaddition followed by 2,2-dioxyoxetane hydrolysis represent useful procedures for Claisen-condensation type, {beta}-hydroxyester synthesis.

  8. Single-Site Zeolite-Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry.

    Science.gov (United States)

    Martinez-Macias, Claudia; Chen, Mingyang; Dixon, David A; Gates, Bruce C

    2015-08-10

    A family of HY zeolite-supported cationic organoiridium carbonyl complexes was formed by reaction of Ir(CO)2 (acac) (acac=acetylacetonate) to form supported Ir(CO)2 complexes, which were treated at 298 K and 1 atm with flowing gas-phase reactants, including C2 H4 , H2 , (12) CO, (13) CO, and D2 O. Mass spectrometry was used to identify effluent gases, and infrared and X-ray absorption spectroscopies were used to characterize the supported species, with the results bolstered by DFT calculations. Because the support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, these were characterized by a high degree of uniformity, which allowed a precise determination of the species involved in the replacement, for example, of one CO ligand of each Ir(CO)2 complex with ethylene. The supported species include the following: Ir(CO)2 , Ir(CO)(C2 H4)2 , Ir(CO)(C2 H4), Ir(CO)(C2 H5), and (tentatively) Ir(CO)(H). The data determine a reaction network involving all of these species.

  9. Photoenolization of o-alkyl-substituted carbonyl compounds. Use of electron transfer processes to characterize transient intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Das, P.K.; Encinas, M.V.; Small, R.D. Jr.; Scaiano, J.C.

    1979-11-07

    Intramolecular hydrogen transfer in photoexcited o-methyl-substituted carbonyl compounds leads to the formation of short-lived biradicals which decay to yield unstable enols. The biradicals can be trapped with suitable electron acceptors, and a study of these processes leads to the measurement of biradical lifetimes, quantum yields, and their rates of electron transfer. The combination of these studies with quenching of the process by 1,3-pentadiene leads to the evaluation of the number and lifetime of the triplet state precursors. Ground-state conformation plays an important role in determining the nature and kinetics of triplet state processes. In a typical example, o-methylbenzaldehyde, two triplet states are responsible for biradical production; they have lifetimes of 1.1 and 95 ns in wet acetonitrile and account for 58% and 42% of the reaction, respectively. The biradicals are generated with a quantum yield of 0.83, live 1500 ns, and transfer an electron to paraquat dications with a rate constant of 6.2 x 10/sup 9/ M/sup -1/s/sup -1/. 5 figures, 2 tables.

  10. Treatment of phenol and p-cresol in aqueous solution by adsorption using a carbonylated hypercrosslinked polymeric adsorbent

    Energy Technology Data Exchange (ETDEWEB)

    Huang Jianhan, E-mail: xiaomeijiangou@yahoo.com.cn [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China)

    2009-09-15

    Phenolic compounds are one of the most representative pollutants in industrial wastewater, and efficient removal and destruction of them have attracted significant concerns. In the present study, a carbonylated hypercrosslinked polymeric adsorbent HJ-1 was developed and its ability to remove phenol and p-cresol in aqueous solution was tested in comparison with the commercial Amberlite XAD-4 resin. The HJ-1 resin exhibited excellent applicability in the acidic and neutral pH, NaCl posed the positive effect, whereas Cd{sup 2+} had the negative effect on the adsorption. The adsorption dynamics obeyed the pseudo-second-order rate equation and the adsorption rate constant of phenol was a little greater than that of p-cresol. The adsorption isotherms can be correlated to Langmuir isotherm and the adsorption capacity of phenol and p-cresol onto HJ-1 resin was much larger than that onto XAD-4. With regard to the two adsorbates, the adsorption capacity of p-cresol was larger than that of phenol at the same temperature and equilibrium concentration. The adsorption thermodynamic parameters were calculated and the adsorption was principally driven by adsorption enthalpy and entropy. Analysis of the different adsorbability of p-cresol from phenol suggested that the solubility and polarity of the adsorbate played important roles.

  11. Effects of Multi-walled Carbon Nanotubes on the Electromagnetic Absorbing Characteristics of Composites Filled with Carbonyl Iron Particles

    Institute of Scientific and Technical Information of China (English)

    Yonggang Xu; Deyuan Zhang; Jun Cai; Liming Yuan; Wenqiang Zhang

    2012-01-01

    The electromagnetic (EM) wave absorbing property of silicone rubber filled with carbonyl iron particles (CIPs) and multi-walled carbon nanotubes (MWCNTs) was examined. Absorbents including MWCNTs and spherical/ flaky CIPs were added to silicone rubber using a two-roll mixer. The complex permittivity and complex permeability were measured over the frequency range of 1-18 GHz. The two EM parameters were verified and the uniform dispersion of MWCNTs and ClPs was confirmed by comparing the measured reflection loss (RL) with the calculated one. As the MWCNT weight percent increased, the RL of the spherical CIPs/silicone rubber composites changed insignificantly. It was attributed to the random distribution of spherical ClPs and less content of MWCNTs. On the contrary, for composites filled with flaky ClPs the absorption bandwidth increased at thickness 0.5 mm (RL value lower than -5 dB in 8-18 GHz) and the absorption ratio increased at lower frequency (minimum -35 dB at 3.5 GHz). This effect was attributed to the oriented distribution of flaky CIPs caused by interactions between the two absorbents. Therefore, mixing MWCNTs and flaky CIPs could achieve wider-band and higher-absorption ratio absorbing materials.

  12. A GREEN APPROACH FOR THE SELECTIVE REDUCTION OF AROMATIC CARBONYL COMPOUNDS USING RANEY Ni-Al ALLOY

    Directory of Open Access Journals (Sweden)

    Mirela Suceveanu

    2016-02-01

    Full Text Available Given the significant environmental risk associated with the use of organic solvents and catalysts in the classic reduction reaction catalysts, we are interested in adapting the reaction medium and in developing an eco-friendly methodology for the synthesis of corresponding alcohols in reasonably yields. In this study, the reduction of some aromatic carbonyl compounds with Ni-Al alloy in aqueous alkaline medium was carried out in two versions: with 20 wt% aq NaOH and with 1 wt% aq NaOH without organic solvent. The structures of the reaction products are rigorously proven by gas chromatography-mass spectrometry (GC-MS. There was observed an increase of the reduction reaction rate when we used 1 wt% aq NaOH without addition of organic solvent. For a good part of the studied substrates high conversion and selectivity were achieved by employing mild reaction conditions, minimal environmental pollution and simple work up procedure, foreshadowing yields above 90 % and representing candidates for convenient preparative applications.

  13. Two-electron reductive carbonylation of terminal uranium(V) and uranium(VI) nitrides to cyanate by carbon monoxide.

    Science.gov (United States)

    Cleaves, Peter A; King, David M; Kefalidis, Christos E; Maron, Laurent; Tuna, Floriana; McInnes, Eric J L; McMaster, Jonathan; Lewis, William; Blake, Alexander J; Liddle, Stephen T

    2014-09-22

    Two-electron reductive carbonylation of the uranium(VI) nitride [U(Tren(TIPS))(N)] (2, Tren(TIPS)=N(CH2CH2NSiiPr3)3) with CO gave the uranium(IV) cyanate [U(Tren(TIPS))(NCO)] (3). KC8 reduction of 3 resulted in cyanate dissociation to give [U(Tren(TIPS))] (4) and KNCO, or cyanate retention in [U(Tren(TIPS))(NCO)][K(B15C5)2] (5, B15C5=benzo-15-crown-5 ether) with B15C5. Complexes 5 and 4 and KNCO were also prepared from CO and the uranium(V) nitride [{U(Tren(TIPS))(N)K}2] (6), with or without B15C5, respectively. Complex 5 can be prepared directly from CO and [U(Tren(TIPS))(N)][K(B15C5)2] (7). Notably, 7 reacts with CO much faster than 2. This unprecedented f-block reactivity was modeled theoretically, revealing nucleophilic attack of the π* orbital of CO by the nitride with activation energy barriers of 24.7 and 11.3 kcal mol(-1) for uranium(VI) and uranium(V), respectively. A remarkably simple two-step, two-electron cycle for the conversion of azide to nitride to cyanate using 4, NaN3 and CO is presented.

  14. The Calvin cycle inevitably produces sugar-derived reactive carbonyl methylglyoxal during photosynthesis: a potential cause of plant diabetes.

    Science.gov (United States)

    Takagi, Daisuke; Inoue, Hironori; Odawara, Mizue; Shimakawa, Ginga; Miyake, Chikahiro

    2014-02-01

    Sugar-derived reactive carbonyls (RCs), including methylglyoxal (MG), are aggressive by-products of oxidative stress known to impair the functions of multiple proteins. These advanced glycation end-products accumulate in patients with diabetes mellitus and cause major complications, including arteriosclerosis and cardiac insufficiency. In the glycolytic pathway, the equilibration reactions between dihydroxyacetone phosphate and glyceraldehyde 3-phosphate (GAP) have recently been shown to generate MG as a by-product. Because plants produce vast amounts of sugars and support the same reaction in the Calvin cycle, we hypothesized that MG also accumulates in chloroplasts. Incubating isolated chloroplasts with excess 3-phosphoglycerate (3-PGA) as the GAP precursor drove the equilibration reaction toward MG production. The rate of oxygen (O2) evolution was used as an index of 3-PGA-mediated photosynthesis. The 3-PGA- and time-dependent accumulation of MG in chloroplasts was confirmed by HPLC. In addition, MG production increased with an increase in light intensity. We also observed a positive linear relationship between the rates of MG production and O2 evolution (R = 0.88; P Calvin cycle and that sugar-derived RC production is inevitable during photosynthesis. Furthermore, we found that MG production is enhanced under high-CO2 conditions in illuminated wheat leaves.

  15. Synthesis and Antimicrobial Activity of N-(6-Carboxyl Cyclohex-3-ene Carbonyl Chitosan with Different Degrees of Substitution

    Directory of Open Access Journals (Sweden)

    Mohamed E. I. Badawy

    2016-01-01

    Full Text Available Five products of N-(6-carboxyl cyclohex-3-ene carbonyl chitosan as antimicrobial agents were prepared by reaction of chitosan with tetrahydrophthalic anhydride (THPA at different degrees of substitution (DS. The antimicrobial activity was evaluated against four plant bacteria and eight fungi. The results proved that the inhibitory property and water solubility of the synthesized chitosan derivatives, with increase of the DS, exhibited a remarkable improvement over chitosan. The product with a DS of 0.40 was the most active one with MIC of 510, 735, 240, and 385 mg/L against Erwinia carotovora, Ralstonia solanacearum, Rhodococcus fascians, and Rhizobium radiobacter, respectively, and also in mycelial growth inhibition against Alternaria alternata (EC50 = 683 mg/L, Botrytis cinerea (EC50 = 774 mg/L, Botryodiplodia theobromae (EC50 = 501 mg/L, Fusarium oxysporum (EC50 = 500 mg/L, F. solani (EC50 = 260 mg/L, Penicillium digitatum (EC50 = 417 mg/L, Phytophthora infestans (EC50 = 298 mg/L, and Sclerotinia sclerotiorum (EC50 = 763 mg/L. These compounds based on a biodegradable and biocompatible chitosan could be used as potentially antimicrobial agents in crop protection instead of hazardous synthetic pesticides.

  16. Protein carbonyl: An oxidative stress marker in gingival crevicular fluid in healthy, gingivitis, and chronic periodontitis subjects

    Directory of Open Access Journals (Sweden)

    Avani R Pradeep

    2013-01-01

    Full Text Available Background: A defined role for reactive oxygen species (ROS in the tissue destruction that characterizes periodontitis has been described. Protein carbonyl (PC is the most widely used biomarker for oxidative damage to proteins, and reflects cellular damage induced by multiple forms of ROS. The purpose of this study is to determine the presence of PC in gingival crevicular fluid (GCF in healthy, gingivitis, and chronic periodontitis (CP subjects and to find an association, if any. Materials and Methods: A total number of 75 subjects (38 males and 37 females were selected based on their clinical parameters into three groups: Group 1 (25 healthy subjects, Group 2 (25 gingivitis subjects, and Group 3 (25 CP subjects. GCF samples were collected to estimate the levels of PC. Results: The PC concentration in GCF was highest in subjects with CP as compared to gingivitis and healthy subjects and a significant association was observed between GCF PC levels and all periodontal parameters. Conclusion: There was an increase in PC levels in GCF as the disease process progressed from healthy to gingivitis and CP, suggesting a role for increased oxidative stress in CP.

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

    Science.gov (United States)

    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.

  18. Complex formation between the uncoupler carbonyl cyanide p-trifluoromethoxyphenylhydrazone (FCCP) and valinomycin in the presence of potassium.

    Science.gov (United States)

    O'Brien, T A; Nieva-Gomez, D; Gennis, R B

    1978-03-25

    Spectroscopic evidence is presented which indicates that the uncoupler carbonyl cyanide p-trifluoromethoxyphenylhydrazone (FCCP) and the peptide antibiotic valinomycin form a complex in the presence of potassium. Complex formation has been observed both in aqueous and nonaqueous media. Several techniques have been used to indicate the existence of a complex in aqueous solution. In the presence of valinomycin and K+, the absorption spectrum of FCCP is significantly perturbed, and there is also a large induced circular dichroism signal. In addition, the previously characterized complex which forms between valinomycin, K+, and the fluorescent probe 8-anilino-1-naphthalene-sulfonate (ANS) in aqueous solution is apparently disrupted by the addition of FCCP. The result is an effective quenching of the fluorescence due to the bound probe as it is displaced from the valinomycin.K+ by the uncoupler. In a nonpolar solvent, the absorption spectrum of FCCP is also perturbed by valinomycin in the presence of K+, again indicating the formation of a complex. These data point to the importance of considering the role of valinomycin.K+.uncoupler complex in interpreting physiological or ion transport data in which these substances have been used together.

  19. Cyclometallated ruthenium(II) carbonyl complexes with 1-pyrenaldehyde 4-R-3-thiosemicarbazones: Regioselective ruthenation of the 1-pyrenyl group

    Indian Academy of Sciences (India)

    Rupesh Narayana Prabhu; Samudranil Pal

    2015-04-01

    A facile method for the synthesis of a series of cyclometallated ruthenium(II) carbonyl complexes with 1-pyrenaldehyde 4-R-3-thiosemicarbazones (H2Ln where the two H’s represent the dissociable thioamide and pyrenyl protons; R = H, Me and Ph) has been described. The characterization of the complexes having the general molecular formula trans-[Ru(Ln)(CO)(EPh33)2] (where E = P or As) were accomplished by elemental (CHN) analysis, magnetic susceptibility and spectroscopic (ESI-MS, IR, UV-Vis, emission and 1H-NMR) measurements. Electronic spectra of the complexes display multiple strong absorptions in the range 440–224 nm due to intraligand transitions. All the complexes exhibit emission bands that are characteristic of ligand centred emissive states. X-ray diffraction studies with representative complexes reveal a pincer-like 5,5-membered fused chelate rings forming CNS coordination mode of the thiosemicarbazonate ligand (Ln)2− via regioselective activation of 1-pyrenyl ortho C–H and formation of a distorted octahedral C2NSE2 coordination sphere around the ruthenium(II) centre.

  20. Heme carbonyls: environmental effects on nu(C-O) and Fe-C/C-O bond length correlations.

    Science.gov (United States)

    Silvernail, Nathan J; Roth, Arne; Schulz, Charles E; Noll, Bruce C; Scheidt, W Robert

    2005-10-19

    The synthesis and characterization of four low-spin (carbonyl)iron(II) tetraphenylporphyrinates, [Fe(TPP)(CO)(L)], where L = 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole (unsolvated), and 1,2-dimethylimidazole (toluene solvate) are reported. The complexes show nearly the same value of nu(C-O) in toluene solution (1969-72 cm(-1)) but a large range of CO stretching frequencies in the solid-state (1926-1968 cm(-1)). The large solid-state variation results from CO interactions in the solid state, as shown by an examination of the crystal structures of the four complexes. The high precision of the four structures obtained allows us to make a number of structural and spectroscopic correlations that describe the Fe-C-O and N(Im)-Fe-CO units. The values of nu(C-O) and the Fe-C and C-O bond distances are strongly correlated and provide a structural, as well as a spectroscopic, correlation of the pi back-bonding model. The interactions of CO described are closely related to the large range of CO stretching frequencies observed in heme proteins and specific interactions observed in carbonylmyoglobin (MbCO).