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Sample records for aldehyde acetals carboxylic

  1. Acetic acid assisted cobalt methanesulfonate catalysed chemoselective diacetylation of aldehydes

    Institute of Scientific and Technical Information of China (English)

    Min Wang; Zhi Guo Song; Hong Gong; Heng Jiang

    2008-01-01

    Cobalt methanesulfonate in combination with acetic acid catalysed the chemoselective diacetylation of aldehyde with acetic anhydride at room temperature under solvent free conditions. After reaction, cobalt methanesulfonate can be easily recovered and mused many times. The reaction was mild and efficient with good to high yields.

  2. Mechanism of catalytic action of oxide systems in reactions of aldehyde oxidation to carboxylic acids

    International Nuclear Information System (INIS)

    Mechanism of selective action of oxide catalysts (on the base of V2O4, MoO3) of aldehyde oxidation to acids is considered, reaction acrolein oxidation to acrylic acid is taken as an example. Multistage mechanism of the process is established; it involves consequent transformation of coordination-bonded aldehyde into carbonyl-bonded aldehyde and symmetric carboxylate. Principles of active surface construction are formulated, they take into account the activity of stabilization center of concrete intermediate compound and bond energy of oxygen with surface. (author)

  3. Aldehydes, ketones, and carboxylic acids formed radiolytically in aqueous solutions of cyanides and simple nitriles

    International Nuclear Information System (INIS)

    A systematic search for aldehydes, ketones, and carboxylic acids was carried out in aqueous solutions of HCN, NH4CN, CH3CN, and C2H4CN, that had received multikilogray doses of 60Co γ radiation. About 30 radiolytic products were identified, among them a large variety of dicarboxylic and tricarboxylic acids. Some of them might be of significant interest in molecular evolution studies of prebiotic processes. They originate in the free-radical-initiated chemical reactions where the additional oligomerization processes are particularly important. Most of the radiolytic products appear in both cyanides and nitriles and point to the importance of reactions involving the carbon-nitrogen triple bond

  4. Aldehydes, ketones, and carboxylic acids formed radiolytically in aqueous solutions of cyanides and simple nitriles

    Energy Technology Data Exchange (ETDEWEB)

    Negron-Mendoza, A.; Draganic, Z.D.; Navarro-Gonzalez, R.; Graganic, I.G.

    1983-08-01

    A systematic search for aldehydes, ketones, and carboxylic acids was carried out in aqueous solutions of HCN, NH/sub 4/CN, CH/sub 3/CN, and C/sub 2/H/sub 4/CN, that had received multikilogray doses of /sup 60/Co ..gamma.. radiation. About 30 radiolytic products were identified, among them a large variety of dicarboxylic and tricarboxylic acids. Some of them might be of significant interest in molecular evolution studies of prebiotic processes. They originate in the free-radical-initiated chemical reactions where the additional oligomerization processes are particularly important. Most of the radiolytic products appear in both cyanides and nitriles and point to the importance of reactions involving the carbon-nitrogen triple bond.

  5. Lewis base activation of Lewis acids. Vinylogous aldol addition reactions of conjugated N,O-silyl ketene acetals to aldehydes.

    Science.gov (United States)

    Denmark, Scott E; Heemstra, John R

    2006-02-01

    N,O-Silyl dienyl ketene acetals derived from unsaturated morpholine amides have been developed as highly useful reagents for vinylogous aldol addition reactions. In the presence of SiCl4 and the catalytic action of chiral phosphoramide (R,R)-3, N,O-silyl dienyl ketene acetal 8 undergoes high-yielding and highly site-selective addition to a wide variety of aldehydes with excellent enantioselectivity. Of particular note is the high yields and selectivities obtained from aliphatic aldehydes. Low catalyst loadings (2-5 mol %) can be employed. The morpholine amide serves as a useful precursor for further synthetic manipulation. PMID:16433495

  6. Oxidation of N-Nitrosoalkylamines by human cytochrome P450 2A6: sequential oxidation to aldehydes and carboxylic acids and analysis of reaction steps.

    Science.gov (United States)

    Chowdhury, Goutam; Calcutt, M Wade; Guengerich, F Peter

    2010-03-12

    Cytochrome P450 (P450) 2A6 activates nitrosamines, including N,N-dimethylnitrosamine (DMN) and N,N-diethylnitrosamine (DEN), to alkyl diazohydroxides (which are DNA-alkylating agents) and also aldehydes (HCHO from DMN and CH(3)CHO from DEN). The N-dealkylation of DMN had a high intrinsic kinetic deuterium isotope effect ((D)k(app) approximately 10), which was highly expressed in a variety of competitive and non-competitive experiments. The (D)k(app) for DEN was approximately 3 and not expressed in non-competitive experiments. DMN and DEN were also oxidized to HCO(2)H and CH(3)CO(2)H, respectively. In neither case was a lag observed, which was unexpected considering the k(cat) and K(m) parameters measured for oxidation of DMN and DEN to the aldehydes and for oxidation of the aldehydes to the carboxylic acids. Spectral analysis did not indicate strong affinity of the aldehydes for P450 2A6, but pulse-chase experiments showed only limited exchange with added (unlabeled) aldehydes in the oxidations of DMN and DEN to carboxylic acids. Substoichiometric kinetic bursts were observed in the pre-steady-state oxidations of DMN and DEN to aldehydes. A minimal kinetic model was developed that was consistent with all of the observed phenomena and involves a conformational change of P450 2A6 following substrate binding, equilibrium of the P450-substrate complex with a non-productive form, and oxidation of the aldehydes to carboxylic acids in a process that avoids relaxation of the conformation following the first oxidation (i.e. of DMN or DEN to an aldehyde). PMID:20061389

  7. Carboxylic Acid Photochemistry is a Marine Source of Glyoxal and Other Aldehydes

    Science.gov (United States)

    Chiu, R.; Gonzalez, L.; Tinel, L.; George, C.; Volkamer, R. M.

    2015-12-01

    Glyoxal is a highly water-soluble precursor in secondary organic aerosol (SOA) formation. Over land, glyoxal is known to be produced by the oxidation of volatile organic carbon (VOC) from both anthropogenic and natural sources. However, marine sources are still not well understood. Previous studies above the remote Pacific Ocean have detected typical glyoxal mixing ratios of 30-40 pptv, concentrations too high to be explained with current chemical understanding or atmospheric models. Because the lifetime of glyoxal is very short, the glyoxal found must have originated from, rather than been transported to, the open ocean. Furthermore, eddy covariance measurements indicate that an organic surface microlayer may be producing the glyoxal by as yet unknown processes. Here we present laboratory studies of the formation of glyoxal from carboxylic acids. Nonanoic, octanoic, and heptanoic acids floated on water and subjected to ultraviolet light are converted into their equivalent alkenals. Subsequent ozonolysis of the alkenals leads to the formation of glyoxal. We employ a PTR-MS to detect the alkenals, and a cavity-enhanced DOAS to detect the glyoxal. Considering the ubiquitous occurrence of carboxylic acids and their derivatives in the environment, this mechanism has the potential to be a significant source of glyoxal in the atmosphere.

  8. The use of anhydrous CeCl{sub 3} as a recyclable and selective catalyst for the acetalization of aldehydes and ketones

    Energy Technology Data Exchange (ETDEWEB)

    Silveira, Claudio C.; Mendes, Samuel R.; Ziembowicz, Francieli I. [Universidade Federal de Santa Maria (UFSM), RS (Brazil). Dept. de Quimica; Lenardao, Eder J.; Perin, Gelson [Universidade Federal de Pelotas (UFPel), RS (Brazil). Inst. de Quimica e Geociencias

    2010-07-01

    An efficient, clean, chemoselective and solvent-free method for the synthesis of ketone and aldehyde dimethyl acetals was developed using trimethyl orthoformate and commercially available anhydrous CeCl{sub 3} as a recyclable catalyst. The method is general and affords the protected carbonyl compounds in good yields and under mild conditions, including aryl and alkyl ketones and activated aldehydes. The catalyst could be utilised directly for 3 cycles, without significant loss of activity. (author)

  9. Benzylidene Acetal Protecting Group as Carboxylic Acid Surrogate: Synthesis of Functionalized Uronic Acids and Sugar Amino Acids.

    Science.gov (United States)

    Banerjee, Amit; Senthilkumar, Soundararasu; Baskaran, Sundarababu

    2016-01-18

    Direct oxidation of the 4,6-O-benzylidene acetal protecting group to C-6 carboxylic acid has been developed that provides an easy access to a wide range of biologically important and synthetically challenging uronic acid and sugar amino acid derivatives in good yields. The RuCl3 -NaIO4 -mediated oxidative cleavage method eliminates protection and deprotection steps and the reaction takes place under mild conditions. The dual role of the benzylidene acetal, as a protecting group and source of carboxylic acid, was exploited in the efficient synthesis of six-carbon sialic acid analogues and disaccharides bearing uronic acids, including glycosaminoglycan analogues. PMID:26572799

  10. A Novel Approach in Cinnamic Acid Synthesis: Direct Synthesis of Cinnamic Acids from Aromatic Aldehydes and Aliphatic Carboxylic Acids in the Presence of Boron Tribromide

    Directory of Open Access Journals (Sweden)

    M. Onciu

    2005-02-01

    Full Text Available Cinnamic acids have been prepared in moderate to high yields by a new direct synthesis using aromatic aldehydes and aliphatic carboxylic acids, in the presence of boron tribromide as reagent, 4-dimethylaminopyridine (4-DMAP and pyridine (Py as bases and N-methyl-2-pyrolidinone (NMP as solvent, at reflux (180-190°C for 8-12 hours.

  11. VO(acac)2 catalyzed condensation of o-phenylenediamine with aromatic carboxylic acids/aldehydes under microwave radiation affording benzimidazoles

    Institute of Scientific and Technical Information of China (English)

    Madhudeepa Dey; Krishnajyoti Deb; Siddhartha Sankar Dhar

    2011-01-01

    Vanadyl acetylacetonate, VO(acac)2, has been found to be very effective catalyst for synthesis of a variety of benzimidazoles under solvent-free condition. The methodology involves the exposure of a mixture of o-phenylenediamine and a selected aromatic carboxylic acid/aldehyde to microwave radiation without the use of any solvent or supporting agents. The benzimidazoles were obtained in quick time with high yields.

  12. Four-component synthesis of 1,3,4-oxadiazole derivatives from N-isocyaniminotriphenylphosphorane, aromatic carboxylic acids, aromatic bis-aldehydes, and secondary amines

    OpenAIRE

    Ramazani, Ali; Karimi, Zahra; SOULDOZI, Ali; AHMADI, Yavar

    2012-01-01

    The 1:1 iminium intermediate generated by the addition of a secondary amine to aromatic bis-aldehydes (isophthalaldehyde and terphthalaldehyde) is trapped by the N-isocyaniminotriphenylphosphorane in the presence of a aromatic carboxylic acid derivative, which leads to the formation of corresponding iminophosphorane intermediate. Then disubstituted 1,3,4-oxadiazole derivatives are formed via intramolecular aza-Wittig reaction of the iminophosphorane intermediates. The reactions were ...

  13. Regioselective Addition of Silyl Enolates to α,β-Unsaturated Aldehyde and its Acetal Catalyzed by MgI2 Etherate

    Institute of Scientific and Technical Information of China (English)

    Xing Xian ZHANG; Wei Dong Z. LI

    2003-01-01

    Regioselective addition reactions of silyl enolates to α,β -unsaturated aldehyde and its acetal catalyzed by MgI2 etherate give aldol adducts (1, 2-addition) preferentially over Michael adducts (1, 4-addition). This unique regioselectivity is distinctly different with other Lewis acidic promoters and may be attributed to the high oxyphilicity of IMg+.

  14. Solvent extraction studies on uranium (VI) with high molecular weight carboxylic acids from acetate medium

    International Nuclear Information System (INIS)

    Carboxylic acids are cation exchanger type of extractant which extract metal ions from weak acidic solutions by ion exchange mechanism. They are present as dimer (H2A2) in the non polar organic diluents. High molecular weight carboxylic acids such as versatic 10 acid and naphthenic acid are used for the separation of high purity of yttrium from heavy fraction of rare earths. Extraction behavior of rare earths with different types of carboxylic acids is also reported. Literature survey revealed that the extraction behavior of uranium from aqueous solutions with carboxylic acids is scanty. An attempt has been made in the present work to examine the extraction behavior of U(VI) with three different types of high molecular weight carboxylic acids namely cekanoic acid, neoheptanoic acid and versatic 10 acid dissolved in xylene. Extraction of metal ions is very much dependent on pH of the solution

  15. Targeted LC-MS derivatization for aldehydes and carboxylic acids with a new derivatization agent 4-APEBA

    NARCIS (Netherlands)

    Eggink, M.; Wijtmans, M.; Kretschmer, A.; Kool, J.; Lingeman, H.; Esch, de I.J.P.; Niessen, W.M.A.; Irth, H.

    2010-01-01

    Based on the template of a recently introduced derivatization reagent for aldehydes, 4-(2-(trimethylammonio)ethoxy)benzeneaminium dibromide (4-APC), a new derivatization agent was designed with additional features for the analysis and screening of biomarkers of lipid peroxidation. The new derivatiza

  16. Targeted LC–MS derivatization for aldehydes and carboxylic acids with a new derivatization agent 4-APEBA

    OpenAIRE

    Eggink, M.; Wijtmans, M; Kretschmer, A.; Kool, J.; Lingeman, H.; Esch, van, H.; Niessen, W.M.A.; Irth, H.

    2010-01-01

    Based on the template of a recently introduced derivatization reagent for aldehydes, 4-(2-(trimethylammonio)ethoxy)benzeneaminium dibromide (4-APC), a new derivatization agent was designed with additional features for the analysis and screening of biomarkers of lipid peroxidation. The new derivatization reagent, 4-(2-((4-bromophenethyl)dimethylammonio)ethoxy)benzenaminium dibromide (4-APEBA) contains a bromophenethyl group to incorporate an isotopic signature to the derivatives and to add add...

  17. Required catalytic properties for alkane production from carboxylic acids: Hydrodeoxygenation of acetic acid

    Institute of Scientific and Technical Information of China (English)

    Zhong; He; Xianqin; Wang

    2013-01-01

    The supported Pt catalysts(1 wt%)were prepared by the incipient impregnation method and analyzed using synchrotron-based X-ray diffraction,BET surface area,oxygen adsorption,CO pulse chemisorption,temperature-programmed desorption(TPD)of acetic acid,H2-TPD,NH3-TPD,O2-TPD,and H2-TPR.The reactivity of Pt-based catalysts was studied using a fixed bed reactor at 300 C and 4 MPa for hydrodeoxygenation of acetic acid,where Pt/TiO2 was very selective for ethane production.TPD experiments revealed that several conditions must be satisfied to achieve this high selectivity to ethane from acetic acid,such as Pt sites,moderate acidity,and medium metal-oxygen bond strength in the oxide support.This work provides insights in developing novel catalytic materials for hydrocarbon productions from various organics including bio-fuels.

  18. Scientific Opinion on the safety and efficacy of straight-chain primary aliphatic alcohols/aldehydes/acids, acetals and esters with esters containing saturated alcohols and acetals containing saturated aldehydes (chemical group 1 when used as flavourings for all animal species

    Directory of Open Access Journals (Sweden)

    EFSA Panel on Additives and Products or Substances used in Animal Feed (FEEDAP

    2013-04-01

    Full Text Available Chemical group 1 (CG 1 consists of straight-chain primary aliphatic alcohols/aldehydes/acids, acetals and esters with esters containing saturated alcohols and acetals containing saturated aldehydes of which 86 are currently authorised for use as flavours in food. The FEEDAP Panel was unable to perform an assessment of ethyl oleate because of its insufficient purity. The following compounds are considered to be safe for all animal species at the use level proposed for feed flavourings: formic acid, acetic acid, propionic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, oleic acid, decanol, dodecanol, decyl acetate and dodecyl acetate. The remaining substances are considered safe for all animal species at 5 mg/kg complete feed (with a margin of safety between 1 and 120 and at 25 mg/kg complete feed (ethyl acetate and hexyl acetate, with a margin of safety between 2 and 6; and at 1 mg/kg complete feed for pigs and poultry and 1.5 mg/kg complete feed for all other species (ethylacrylate, ethyl hex-3-enoate, ethyl trans-2-butenoate, ethyl isobutyrate, ethyl isovalerate, butyl isovalerate, methyl isovalerate, hexyl isobutyrate, methyl 2-methyl butyrate, pentyl isovalerate, butyl 2-methyl butyrate, hexyl isovalerate, ethyl 2-methyl butyrate, hexyl 2-methyl butyrate and methyl 2-methylvalerate. No safety concern would arise for the consumer from the use of compounds belonging to CG 1 up to the highest safe level in feedingstuffs for all animal species. The FEEDAP Panel considers it prudent to treat all compounds under assessment as irritants to skin, eyes and respiratory tract and as skin sensitizers. No risk for the safety for the environment is foreseen. Since all 85 compounds are used in food as flavourings, no further demonstration of efficacy is necessary.

  19. Scientific Opinion on the safety and efficacy of branched-chain primary aliphatic alcohols/aldehydes/acids, acetals and esters with esters containing branched-chain alcohols and acetals containing branched-chain aldehydes (chemical group 2 when used as flavourings for all animal species

    Directory of Open Access Journals (Sweden)

    EFSA Panel on Additives and Products or Substances used in Animal Feed (FEEDAP

    2012-10-01

    Full Text Available

    Chemical group 2 consists of branched-chain primary aliphatic alcohols/aldehydes/acids, acetals and esters with esters containing branched-chain alcohols and acetals containing branched-chain aldehydes, of which 34 are currently authorised for use as flavours in food. The use of 2-methylpropionic acid, isopentyl acetate, 3-methylbutyl butyrate and 2-methylbutyl acetate is safe at the proposed use level of 25 mg/kg complete feed for cattle, salmonids and non food producing animals and at 5 mg/kg complete feed for pigs and poultry. 2-Methylpropan-1-ol, isopentanol, 2-ethylhexan-1-ol, 2-methylpropanal, 3-methylbutanal, 2-methylbutyraldehyde, 3-methylbutyric acid, 2-methylvaleric acid, 2-ethylbutyric acid, 2-methylbutyric acid, 2-methylheptanoic acid, 4-methyloctanoic acid, isobutyl acetate, isobutyl butyrate, 3-methylbutyl propionate, 3-methylbutyl formate, glyceryl tributyrate, isobutyl isobutyrate, isopentyl isobutyrate, isobutyl isovalerate, isopentyl 2-methylbutyrate, 2-methylbutyl isovalerate and 2-methylbutyl butyrate are safe at the proposed use level of 5 mg/kg complete feed for all animal species. 3,7-Dimethyloctan-1-ol, 2-methylundecanal, 4-methylnonanoic acid, 3-methylbutyl hexanoate, 3-methylbutyl dodecanoate, 3-methylbutyl octanoate and 3-methylbutyl 3-methylbutyrate are safe at a maximum of 1.5 mg/kg complete feed for cattle, salmonids and non food-producing animals and of 1.0 mg/kg complete feed for pigs and poultry. No safety concern was identified for the consumer from the use of these compounds up to the highest safe level in feedingstuffs for all animal species. All compounds should be considered as irritants to skin, eyes and respiratory tract, and as skin sensitisers. The compounds do not pose a risk to the environment when used at concentrations considered safe for the target species. Since all compounds are used in food as flavourings, no further demonstration of efficacy is necessary.

  20. Mechanism of Alcohol-Water Dehydrogenative Coupling into Carboxylic Acid Using Milstein's Catalyst: A Detailed Investigation of the Outer-Sphere PES in the Reaction of Aldehydes with an Octahedral Ruthenium Hydroxide.

    Science.gov (United States)

    Hasanayn, Faraj; Al-Assi, Lara M; Moussawi, Rasha N; Omar, Boushra Srour

    2016-08-15

    In aqueous basic media, the square-pyramidal complex [Ru(PNN)(CO)(H)] (1-Ru, where PNN is a dearomatized bipyridyl-CH-P(t)Bu2 pincer ligand) catalyzes the transformation of alcohols and water into carboxylates and H2. A previous theoretical investigation reported the following mechanism for the reaction: (i) metal-catalyzed dehydrogenation of the alcohol into an aldehyde, (ii) metal-ligand cooperation (MLC) addition of water to 1-Ru to give an octahedral ruthenium hydroxide (2-Ru-OH), (iii) concerted MLC hydration of the aldehyde by 2-Ru-OH to give separated 1-Ru and a gem-diol, and (iv) concerted MLC dehydrogenation of the gem-diol by 1-Ru into an octahedral ruthenium dihydride (2-Ru-H) and a carboxylic acid. We calculate the outer-sphere PES in the reaction between the aldehyde and 2-Ru-OH to start with a localized coupling step yielding an ion-pair minimum (7-ip-OH) in which the hydroxyl group of an α-hydroxyl-alkoxide (gem-diolate) is coordinated to the metal of a cationic square-pyramidal complex. From 7-ip-OH, we identify a route to carboxylic acid that circumvents ligand deprotonation involving (i) 1,1-rearrangement of the gem-diolate within the contact ion pair through an α-OH/O(-) slippage TS into the octahedral 2-Ru-OCH(OH)R and (ii) a second 1,1-rearrangement through an α-O(-)/H slippage TS that gives a new ion-pair minimum in which the α-hydrogen of the anion is coordinated to the metal, followed by a localized hydride-transfer TS that gives a carboxylic acid and the octahedral hydride complex (2-Ru-H). The net transformation from 2-Ru-OH and the aldehyde to the carboxylic acid and 2-Ru-H can be viewed as a H/OH metathesis in which a hydride and a hydroxide are exchanged between the acyl group of the aldehyde and the metal center of 2-Ru-OH. The MLC mechanism gives the same metathesis products through the intermediacy of a gem-diol. When the SMD solvent continuum model is applied during geometry optimization with water as the solvent, the Gibbs free

  1. Organic acids and aldehydes in rainwater in a northwest region of Spain

    Energy Technology Data Exchange (ETDEWEB)

    Pena, R.M.; Garcia, S.; Herrero, C. [Universidad de Santiago de Compostela, Lugo (Spain). Departamento de Quimica Analitica, Nutricion y Bromatologia

    2002-11-01

    During a 1 year period, measurements of carboxylic acids and aldehydes were carried out in rainwater samples collected at nine different sites in NW Spain surrounding a thermal power plant in order to determine concentration levels and sources. In addition, certain major ions (Cl{sup -}, NO{sub 3}{sup -}, SO{sub 4}{sup 2-}, Na{sup +}, NH{sub 4}{sup +}, K{sup +}, Mg{sup 2+}, Ca{sup 2+}) were also determined. Aldehyde and carboxylic acid concentration patterns and their effects on rainwater composition concerning temporal, seasonal and spatial variations were evaluated. Among carboxylic acids, formic and acetic were predominant (VWA 7.0 and 8.3 {mu}M), while formaldehyde and acroleine were the dominant aldehydes (VWA 0.42 and 1.25 {mu}M). Carboxylic acids were estimated to account for 27.5% of the total free acidity (TFA), whereas sulphuric and nitric acid accounted for 46.2% and 26.2%, respectively. Oxalic acid was demonstrated to be an important contributing compound to the acidification in rainwater representing 7.1% of the TFA. The concentration of aldehydes and carboxylic acids, which originated mainly from biogenic emissions in the area studied, was strongly dependent on the season of the year (growing and non-growing). The ratios of formic to acetic acids are considerably different in the two seasons suggesting that there exist distinct sources in both growing and non-growing seasons. Principal component analysis was applied in order to elucidate the sources of aldehydes and organic acids in rainwater. The prevalence of natural vegetative origins for both of these compounds versus anthropogenic emissions was demonstrated and the importance of the oxidation of aldehydes as a relevant source of organic acids was also established. (author)

  2. CuO and Ag2O/CuO Catalyzed Oxidation of Aldehydes to the Corresponding Carboxylic Acids by Molecular Oxygen

    OpenAIRE

    Yaowu Sha; Daxin Shi; Qingyong Tian

    2008-01-01

    Furfural was oxidized to furoic acid by molecular oxygen under catalysis by 150nm-sized Ag2O/CuO (92%) or simply CuO (86.6%). When 30 nm-size catalyst was used,the main product was a furfural Diels-Alder adduct. Detailed reaction conditions andregeneration of catalysts were investigated. Under optimal conditions, a series of aromaticand aliphatic aldehydes were oxidized to the corresponding acids in good yields.

  3. CuO and Ag2O/CuO Catalyzed Oxidation of Aldehydes to the Corresponding Carboxylic Acids by Molecular Oxygen

    Directory of Open Access Journals (Sweden)

    Yaowu Sha

    2008-04-01

    Full Text Available Furfural was oxidized to furoic acid by molecular oxygen under catalysis by 150nm-sized Ag2O/CuO (92% or simply CuO (86.6%. When 30 nm-size catalyst was used,the main product was a furfural Diels-Alder adduct. Detailed reaction conditions andregeneration of catalysts were investigated. Under optimal conditions, a series of aromaticand aliphatic aldehydes were oxidized to the corresponding acids in good yields.

  4. EFSA ; Scientific Opinion on Flavouring Group Evaluation 67, Revision 1 (FGE.67Rev.1): Consideration of 40 furan-substituted aliphatic hydrocarbons, alcohols, aldehydes, ketones, carboxylic acids and related esters, sulfides, disulfides and ethers evaluated by JECFA at the 65th meeting (JECFA, 2006

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister; Lund, Pia; Binderup, Mona-Lise

    evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 33 furan-substituted aliphatic hydrocarbons, alcohols, aldehydes, ketones, carboxylic acids and related esters, sulfides, disulfides and ethers evaluated by the JECFA. In the...

  5. Double stereodifferentiation in the "acetate-type" aldol reaction with garner's aldehyde. Stereocontrolled synthesis of polyhydroxylated gamma-amino carbonyl compounds.

    Science.gov (United States)

    Vicario, Jose L; Rodriguez, Mónica; Badía, Dolores; Carrillo, Luisa; Reyes, Efraim

    2004-09-01

    [reaction: see text] The aldol reaction of acetamide enolates with protected chiral alpha-amino-beta-hydroxy aldehyde 1 (Garner's aldehyde) has been performed in a stereocontrolled way under double stereodifferentiation conditions using pseudoephedrine as the additional chiral information source attached to the enolate reagent. In addition, the obtained adduct has been transformed into other valuable chiral building blocks such as gamma-amino-beta,delta-dihydroxy acids, esters, and ketones. PMID:15330615

  6. Oxidation of N-Nitrosoalkylamines by Human Cytochrome P450 2A6: SEQUENTIAL OXIDATION TO ALDEHYDES AND CARBOXYLIC ACIDS AND ANALYSIS OF REACTION STEPS*

    OpenAIRE

    Chowdhury, Goutam; Calcutt, M. Wade; Guengerich, F. Peter

    2010-01-01

    Cytochrome P450 (P450) 2A6 activates nitrosamines, including N,N-dimethylnitrosamine (DMN) and N,N-diethylnitrosamine (DEN), to alkyl diazohydroxides (which are DNA-alkylating agents) and also aldehydes (HCHO from DMN and CH3CHO from DEN). The N-dealkylation of DMN had a high intrinsic kinetic deuterium isotope effect (Dkapp ∼ 10), which was highly expressed in a variety of competitive and non-competitive experiments. The Dkapp for DEN was ∼3 and not expressed in non-competitive experiments. ...

  7. Role of pseudoephedrine as chiral auxiliary in the "acetate-type" aldol reaction with chiral aldehydes; asymmetric synthesis of highly functionalized chiral building blocks.

    Science.gov (United States)

    Ocejo, Marta; Carrillo, Luisa; Vicario, Jose L; Badía, Dolores; Reyes, Efraim

    2011-01-21

    We have studied in depth the aldol reaction between acetamide enolates and chiral α-heterosubstituted aldehydes using pseudoephedrine as chiral auxiliary under double stereodifferentiation conditions, showing that high diastereoselectivities can only be achieved under the matched combination of reagents and provided that the α-heteroatom-containing substituent of the chiral aldehyde is conveniently protected. Moreover, the obtained highly functionalized aldols have been employed as very useful starting materials for the stereocontrolled preparation of other interesting compounds and chiral building blocks such as pyrrolidines, indolizidines, and densely functionalized β-hydroxy and β-amino ketones using simple and high-yielding methodologies. PMID:21188970

  8. Beyond ketonization: selective conversion of carboxylic acids to olefins over balanced Lewis acid–base pairs

    Energy Technology Data Exchange (ETDEWEB)

    Baylon, Rebecca A. L.; Sun, Junming; Martin, Kevin J.; Venkitasubramanian, Padmesh; Wang, Yong

    2016-01-01

    Dwindling petroleum reserves combined with increased energy demand and political factors encouraging an increase in energy independence have led to a large amount of research on sustainable alternatives. To this end, biomass conversion has been recognized as themost readily viable technology to produce biofuel concerning our reliance on liquid fuels for transportation and has the advantage of being easily integrated into our heavy use of combustion engines. The interest in biomass conversion has also resulted in reduced costs and a greater abundance of bio-oil, a mixture of hundreds of oxygenates including alcohols, aldehydes, carboxylic acids, and ketones. However, the presence of carboxylic acids in bio-oil derived from lignocellulose pyrolysis leads to low pH, instability, and corrosiveness. In addition, carboxylic acids (i.e. acetic acid) can also be produced via fermentation of sugars. This can be accomplished by a variety of homoacetogenic microorganisms that can produce acetic acid with 100% carbon yield.

  9. Biomimetic Decarboxylation of Carboxylic Acids with PhI(OAc)2 Catalyzed by Manganese Porphyrin [Mn(TPP)OAcl

    Institute of Scientific and Technical Information of China (English)

    GHOLAM REZA Karimipour; ROXANA Ahmadpour

    2008-01-01

    Manganese(Ⅲ) meso-tetraphenylporphyrin acetate [Mn(TPP)OAc] served as an effective catalyst for the oxidative decarboxylation of carboxylic acids with (diacetoxyiodo)benzene [Phl(OAc)2] in CH2C12-H2O(95:5,volume ratio),The aryl substituted acetic acids are more reactive than the less electron rich linear carboxylic acids in the presence of catalyst Mn(TPP)OAc,In the former case,the formation of carbonyl products was complete within just a few minutes with >97% selectivities,and no further oxidation of the produced aldehydes was achieved under these catalytic conditions,This method provides a benign procedure owing to the utilization of low toxic(diacetoxyiodo)benzene,biologically relevant manganese porphyrins,and carboxylic acids.

  10. Synthesis of 5'-Aldehyde Oligonucleotide.

    Science.gov (United States)

    Lartia, Rémy

    2016-01-01

    Synthesis of oligonucleotide ending with an aldehyde functional group at their 5'-end (5'-AON) is possible for both DNA (5'-AODN) and RNA (5'-AORN) series irrespectively of the nature of the last nucleobase. The 5'-alcohol of on-support ODN is mildly oxidized under Moffat conditions. Transient protection of the resulting aldehyde by N,N'-diphenylethylenediamine derivatives allows cleavage, deprotection, and RP-HPLC purification of the protected 5'-AON. Finally, 5'-AON is deprotected by usual acetic acid treatment. In the aggregates, 5'-AON can be now synthesized and purified as routinely as non-modified ODNs, following procedures similar to the well-known "DMT-On" strategy. PMID:26967469

  11. Exploring the reductive capacity of Pyrococcus furiosus. The reduction of carboxylic acids and pyridine nucleotides

    OpenAIRE

    Ban, van den, A.W.

    2001-01-01

    This Ph.D. project started in 1997 and its main goal was to obtain insight in the reductive capacity of the hyperthermophilic archaeon Pyrococcus furiosus . The research was focused on the biocatalytic reduction of carboxylic acids.Reductions of carboxylic acids are interesting reactions, since the generated products, aldehydes and alcohols, are potentially applicable in the fine-chemical industry. However, the reduction of carboxylic acids to the corresponding aldehydes is a thermodynamicall...

  12. Volatile aldehydes in libraries and archives

    Science.gov (United States)

    Fenech, Ann; Strlič, Matija; Kralj Cigić, Irena; Levart, Alenka; Gibson, Lorraine T.; de Bruin, Gerrit; Ntanos, Konstantinos; Kolar, Jana; Cassar, May

    2010-06-01

    Volatile aldehydes are produced during degradation of paper-based materials. This may result in their accumulation in archival and library repositories. However, no systematic study has been performed so far. In the frame of this study, passive sampling was carried out at ten locations in four libraries and archives. Despite the very variable sampling locations, no major differences were found, although air-filtered repositories were found to have lower concentrations while a non-ventilated newspaper repository exhibited the highest concentrations of volatile aldehydes (formaldehyde, acetaldehyde, furfural and hexanal). Five employees in one institution were also provided with personal passive samplers to investigate employees' exposure to volatile aldehydes. All values were lower than the presently valid exposure limits. The concentration of volatile aldehydes, acetic acid, and volatile organic compounds (VOCs) in general was also compared with that of outdoor-generated pollutants. It was evident that inside the repository and particularly inside archival boxes, the concentration of VOCs and acetic acid was much higher than the concentration of outdoor-generated pollutants, which are otherwise more routinely studied in connection with heritage materials. This indicates that further work on the pro-degradative effect of VOCs on heritage materials is necessary and that monitoring of VOCs in heritage institutions should become more widespread.

  13. Transcriptome analysis of Zymomonas mobilis ZM4 reveals mechanisms of tolerance and detoxification of phenolic aldehyde inhibitors from lignocellulose pretreatment

    OpenAIRE

    Yi, Xia; Gu, Hanqi; Gao, Qiuqiang; Liu, Z. Lewis; Bao, Jie

    2015-01-01

    Background Phenolic aldehydes generated from lignocellulose pretreatment exhibited severe toxic inhibitions on microbial growth and fermentation. Numerous tolerance studies against furfural, 5-hydroxymethyl-2-furaldehyde (HMF), acetate, and ethanol were reported, but studies on inhibition of phenolic aldehyde inhibitors are rare. For ethanologenic strains, Zymomonas mobilis ZM4 is high in ethanol productivity and genetic manipulation feasibility, but sensitive to phenolic aldehyde inhibitors....

  14. The roles of aldehyde dehydrogenases (ALDHs in the PDH bypass of Arabidopsis

    Directory of Open Access Journals (Sweden)

    Lin Ming

    2009-03-01

    Full Text Available Abstract Background Eukaryotic aldehyde dehydrogenases (ALDHs, EC 1.2.1, which oxidize aldehydes into carboxylic acids, have been classified into more than 20 families. In mammals, Family 2 ALDHs detoxify acetaldehyde. It has been hypothesized that plant Family 2 ALDHs oxidize acetaldehyde generated via ethanolic fermentation, producing acetate for acetyl-CoA biosynthesis via acetyl-CoA synthetase (ACS, similar to the yeast pathway termed the "pyruvate dehydrogenase (PDH bypass". Evidence for this pathway in plants has been obtained from pollen. Results To test for the presence of the PDH bypass in the sporophytic tissue of plants, Arabidopsis plants homozygous for mutant alleles of all three Family 2 ALDH genes were fed with 14C-ethanol along with wild type controls. Comparisons of the incorporation rates of 14C-ethanol into fatty acids in mutants and wild type controls provided direct evidence for the presence of the PDH bypass in sporophytic tissue. Among the three Family 2 ALDHs, one of the two mitochondrial ALDHs (ALDH2B4 appears to be the primary contributor to this pathway. Surprisingly, single, double and triple ALDH mutants of Arabidopsis did not exhibit detectable phenotypes, even though a Family 2 ALDH gene is required for normal anther development in maize. Conclusion The PDH bypass is active in sporophytic tissue of plants. Blocking this pathway via triple ALDH mutants does not uncover obvious visible phenotypes.

  15. Cyclodextrin derivatives with cyanohydrin and carboxylate groups as artificial glycosidases

    DEFF Research Database (Denmark)

    Bols, Mikael; Ortega-Caballero, Fernando

    2006-01-01

    Two cyclodextrin derivatives (1 and 2) were prepared in an attempt to create glycosidase mimics with a general acid catalyst and a nucleophilic carboxylate group. The catalysts 1 and 2 were found to catalyse the hydrolysis of 4-nitrophenyl beta-D-glucopyranoside at pH 8.0, but rapidly underwent...... decomposition with loss of hydrogen cyanide to convert the cyanohydrin to the corresponding aldehyde. The initial rate of the catalysis shows that the cyanohydrin group in these molecules functions as a good catalyst, but that the carboxylate has no positive effect. The decomposition product aldehydes display...

  16. Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

    1998-12-31

    A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

  17. Soluble aldehyde dehydrogenase and metabolism of aldehydes by soybean bacteroids.

    OpenAIRE

    Peterson, J. B.; LaRue, T A

    1982-01-01

    A soluble aldehyde dehydrogenase (EC 1.2.1.3) was partially purified from Rhizobium japonicum bacteroids and from free-living R. japonicum 61A76. The enzyme was activated by NAD+, NADH, and dithiothreitol, and it reduced NAD(P)+. Acetaldehyde, propionaldehyde, butyraldehyde, benzaldehyde, and succinic semialdehyde were substrates. The Km for straight-chain aldehydes decreased with increasing carbon chain length. The aldehyde dehydrogenase was inhibited by 6-cyanopurine, but not by metronidazo...

  18. Transcriptome analysis of Zymomonas mobilis ZM4 reveals mechanisms of tolerance and detoxification of phenolic aldehyde inhibitors from lignocellulose pretreatment

    Science.gov (United States)

    Background: Phenolic aldehydes generated from lignocellulose pretreatment exhibited severe toxic inhibitions on microbial growth and fermentation. Numerous tolerance studies against furfural, 5-hydroxymethyl-2-furaldehyde (HMF), acetate, and ethanol were reported, but studies on inhibition of phenol...

  19. Applications of Carboxylic Acid Reductases in Oleaginous Microbes

    Energy Technology Data Exchange (ETDEWEB)

    Resch, Michael G.; Linger, Jeffrey; McGeehan, John; Tyo, Keith; Beckham, Gregg

    2016-04-24

    Carboxylic acid reductases (CARs) are recently emerging reductive enzymes for the direct production of aldehydes from biologically-produced carboxylic acids. Recent work has demonstrated that these powerful enzymes are able to reduce a very broad range of volatile- to long-chain fatty acids as well as aromatic acids. Here, we express four CAR enzymes from different fungal origins to test their activity against fatty acids commonly produced in oleaginous microbes. These in vitro results will inform metabolic engineering strategies to conduct mild biological reduction of carboxylic acids in situ, which is conventionally done via hydrotreating catalysis at high temperatures and hydrogen pressures.

  20. Selective Enzymatic Reduction of Aldehydes

    Directory of Open Access Journals (Sweden)

    Patrizia Di Gennaro

    2006-05-01

    Full Text Available Highly selective enzymatic reductions of aldehydes to the corresponding alcohols was performed using an E. coli JM109 whole cell biocatalyst. A selective enzymatic method for the reduction of aldehydes could provide an eco-compatible alternative to chemical methods. The simplicity, fairly wide scope and the very high observed chemoselectivity of this approach are its most unique features.

  1. The profile of volatile compounds in the outer and inner parts of broiled pork neck is strongly influenced by the acetic-acid marination conditions.

    Science.gov (United States)

    Biller, Elżbieta; Boselli, Emanuele; Obiedziński, Mieczysław; Karpiński, Piotr; Waszkiewicz-Robak, Bożena

    2016-11-01

    Raw pork neck cutlets were marinated in an aqueous solution of acetic acid (pH4, 24h, 4°C) without (M) or with 1% (w/w) of glucose. The control (K) was formed by non-treated raw pork neck. The cutlets were then broiled (185°C, 30min). In all K cutlets, significant higher amounts of volatile compounds (VCs) were developed after broiling than the other samples. Significant more aldehydes and alcohols were present in the inner parts than in the surface. The correlation between surface and internal layers was high only for aldehydes. Marinating decreased the differences among VCs and led to the standardization of the processed meat. The addition of glucose to the marinade led to more volatile aldehydes, carboxylic acids, esters, furan, pyran, pyrazine, pyrrol and pyridine derivatives than in M samples. Several (53) specific VCs explained the differences among the surface samples related to the marinating process. However, only 16 VCs explained the variance among the inner parts. PMID:27395822

  2. Carboxylic ester hydrolases in mitochondria from rat skeletal muscle

    DEFF Research Database (Denmark)

    Kirkeby, S; Moe, D; Zelander, T

    1990-01-01

    organophosphate and organomercury. The activity of the indoxyl acetate esterases was enhanced by the non-ionic detergents Tween-40 and Lubrol. After freezing, thawing and high speed centrifugation most of the alpha-naphthyl acetate splitting enzymes were found in the supernatant, indicating that the enzymes are......A mitochondrial pellet, prepared from rat skeletal muscle, contained a number of carboxylic ester hydrolase isoenzymes. The esterases which split alpha-naphthyl acetate were organophosphate sensitive, whereas two out of three indoxyl acetate hydrolysing enzymes were resistant to both...

  3. Acetate catabolism by Methanosarcina barkeri

    International Nuclear Information System (INIS)

    Cell suspensions of Methanosarcina barkeri convert the carboxyl and methyl group carbons of acetate to carbon dioxide and methane at pH 6 under an atmosphere of 100% CO2. The rate of loss of radioactivity from [1-14C]acetate was over three times greater than that from [2-14C]acetate under these conditions. Control experiments with both labeled substrates present showed that the rates were additive. Addition of a high level of 2-bromoethanesulfonate to selectively inhibit methane formation largely inhibited release of 14C from methyl-labeled acetate but only marginally decreased the rate of loss from [1-14C]acetate. Thus, in the absence of the inhibitor loss of 14C from [1-14C]acetate likely reflects an isotopic exchange reaction with CO2 superimposed on the overall conversion of acetate to CO2 and CH4. The exchange reaction was inhibited by uncouplers such as 2,4-dinitrophenol, CCCP, and FCCP. Cells permeabilized by treatment with nonionic detergents or disrupted by passage through a French pressure cell failed to catalyze the exchange reaction. Exchange activity was not restored by addition of ATP or by use of [1-14C]acetyl CoA as substrate. No evidence for involvement of carbon monoxide dehydrogenase in the exchange was found in these experiments when CO2 was replaced by CO. However, the soluble extracts retained the ability to convert acetate to methane in the presence of H2 and ATP

  4. Critical Design Features of Phenyl Carboxylate-Containing Polymer Microbicides

    OpenAIRE

    Rando, Robert F.; Obara, Sakae; Osterling, Mark C.; Mankowski, Marie; Miller, Shendra R.; Ferguson, Mary L.; Krebs, Fred C.; Wigdahl, Brian; Labib, Mohamed; Kokubo, Hiroyasu

    2006-01-01

    Recent studies of cellulose-based polymers substituted with carboxylic acids like cellulose acetate phthalate (CAP) have demonstrated the utility of using carboxylic acid groups instead of the more common sulfate or sulfonate moieties. However, the pKa of the free carboxylic acid group is very important and needs careful selection. In a polymer like CAP the pKa is approximately 5.28. This means that under the low pH conditions found in the vaginal lumen, CAP would be only minimally soluble an...

  5. Contamination of Acetic and Formic Acids in Water and Its Implications for the Study of Carboxylic Acids in Snow and Ice%超纯水中甲酸、乙酸污染的实验研究及其对雪冰有机酸测定的意义

    Institute of Scientific and Technical Information of China (English)

    姚檀栋; 孙维贞; 蒲健长; 田立德; 焦克勤

    2000-01-01

    the carboxylic acids. The acetic acid contamination due to thermal plastic seal is about 18 times higher than that of formic acid under the same conditions. Additionally, the air is another contributor of formic acid and acetic acid to water samples, the contamination of which are much less than of the plastic bag. Consequently, the study of the carboxylic acids in snow and ice must avoid the plastic containers, especially the polyethylene bags, in the processes of sample preparations.

  6. Palladium-Catalyzed C–C Bond Formations via Activation of Carboxylic Acids and Their Derivatives

    OpenAIRE

    Song, Bingrui

    2013-01-01

    Applications of carboxylic acids and their derivatives in transition metal-catalyzed cross-coupling reactions regio-selectively forming Csp3-Csp2, and Csp2-Csp2 bonds were explored in this thesis. Several important organic building blocks such as aryl acetates, diaryl acetates, imines, ketones, biaryls, styrenes and polysubstituted alkenes were successfully accessed from carboxylic acids and their derivatives by the means of C–H activation and decarboxylative cross-couplings. An efficient ...

  7. Hygroscopic Characteristics of Alkylaminium Carboxylate Aerosols.

    Science.gov (United States)

    Gomez-Hernandez, Mario; McKeown, Megan; Secrest, Jeremiah; Marrero-Ortiz, Wilmarie; Lavi, Avi; Rudich, Yinon; Collins, Don R; Zhang, Renyi

    2016-03-01

    The hygroscopic growth factor (HGF) and cloud condensation nuclei (CCN) activity for a series of alkylaminium carboxylate aerosols have been measured using a hygroscopicity tandem differential mobility analyzer coupled to a condensation particle counter and a CCN counter. The particles, consisting of the mixtures of mono- (acetic, propanoic, p-toluic, and cis-pinonic acid) and dicarboxylic (oxalic, succinic, malic, adipic, and azelaic acid) acid with alkylamine (mono-, di-, and trimethylamines), represent those commonly found under diverse environmental conditions. The hygroscopicity parameter (κ) of the alkylaminium carboxylate aerosols was derived from the HGF and CCN results and theoretically calculated. The HGF at 90% RH is in the range of 1.3 to 1.8 for alkylaminium monocarboxylates and 1.1 to 2.2 for alkylaminium dicarboxylates, dependent on the molecular functionality (i.e., the carboxylic or OH functional group in organic acids and methyl substitution in alkylamines). The κ value for all alkylaminium carboxylates is in the range of 0.06-1.37 derived from the HGF measurements at 90% RH, 0.05-0.49 derived from the CCN measurements, and 0.22-0.66 theoretically calculated. The measured hygroscopicity of the alkylaminium carboxylates increases with decreasing acid to base ratio. The deliquescence point is apparent for several of the alkylaminium dicarboxylates but not for the alkylaminium monocarboxylates. Our results reveal that alkylaminium carboxylate aerosols exhibit distinct hygroscopic and deliquescent characteristics that are dependent on their molecular functionality, hence regulating their impacts on human health, air quality, and direct and indirect radiative forcing on climate. PMID:26794419

  8. Process for producing furan from furfural aldehyde

    Science.gov (United States)

    Diebold, James P.; Evans, Robert J.

    1988-01-01

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

  9. Microsphere coated substrate containing reactive aldehyde groups

    Science.gov (United States)

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

    1984-01-01

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

  10. Synthesis and accumulation of aromatic aldehydes in an engineered strain of Escherichia coli.

    Science.gov (United States)

    Kunjapur, Aditya M; Tarasova, Yekaterina; Prather, Kristala L J

    2014-08-20

    Aromatic aldehydes are useful in numerous applications, especially as flavors, fragrances, and pharmaceutical precursors. However, microbial synthesis of aldehydes is hindered by rapid, endogenous, and redundant conversion of aldehydes to their corresponding alcohols. We report the construction of an Escherichia coli K-12 MG1655 strain with reduced aromatic aldehyde reduction (RARE) that serves as a platform for aromatic aldehyde biosynthesis. Six genes with reported activity on the model substrate benzaldehyde were rationally targeted for deletion: three genes that encode aldo-keto reductases and three genes that encode alcohol dehydrogenases. Upon expression of a recombinant carboxylic acid reductase in the RARE strain and addition of benzoate during growth, benzaldehyde remained in the culture after 24 h, with less than 12% conversion of benzaldehyde to benzyl alcohol. Although individual overexpression results demonstrated that all six genes could contribute to benzaldehyde reduction in vivo, additional experiments featuring subset deletion strains revealed that two of the gene deletions were dispensable under the conditions tested. The engineered strain was next investigated for the production of vanillin from vanillate and succeeded in preventing formation of the byproduct vanillyl alcohol. A pathway for the biosynthesis of vanillin directly from glucose was introduced and resulted in a 55-fold improvement in vanillin titer when using the RARE strain versus the wild-type strain. Finally, synthesis of the chiral pharmaceutical intermediate L-phenylacetylcarbinol (L-PAC) was demonstrated from benzaldehyde and glucose upon expression of a recombinant mutant pyruvate decarboxylase in the RARE strain. Beyond allowing accumulation of aromatic aldehydes as end products in E. coli, the RARE strain expands the classes of chemicals that can be produced microbially via aldehyde intermediates. PMID:25076127

  11. A Comparative 90 Day Toxicity Study of Allyl Acetate, Allyl Alcohol and Acrolein

    OpenAIRE

    Auerbach, Scott S.; Mahler, Joel; Travlos, Gregory S.; Irwin, Richard D

    2008-01-01

    Allyl acetate (AAC), allyl alcohol (AAL), and acrolein (ACR) are used in the manufacture of detergents, plastics, pharmaceuticals, and chemicals and as agricultural agents. A metabolic relationship exists between these chemicals in which allyl acetate is metabolized to allyl alcohol and subsequently to the highly reactive,α,β-unsaturated aldehyde, acrolein. Due to the weaker reactivity of the protoxicants, allyl acetate and allyl alcohol, relative to acrolien we hypothesized the protoxicants ...

  12. Metal extraction by amides of carboxylic acids

    International Nuclear Information System (INIS)

    Extraction ability of various amides was studied. Data on extraction of rare earths, vanadium, molybdenum, rhenium, uranium, niobium, tantalum by N,N-dibutyl-amides of acetic, nonanic acids and fatly synthetic acids of C7-C9 fractions are presented. Effect of salting-out agents, inorganic acid concentrations on extraction process was studied. Potential ability of using amides of carboxylic acids for extractional concentration of rare earths as well as for recovery and separation of iron, rhenium, vanadium, molybdenum, uranium, niobium, and tantalum was shown

  13. Formal [4+2] cycloaddition of di-tert-butyl 2-ethoxycyclobutane-1,1-dicarboxylate with ketones or aldehydes and tandem lactonization.

    Science.gov (United States)

    Okado, Ryohei; Nowaki, Aya; Matsuo, Jun-Ichi; Ishibashi, Hiroyuki

    2012-01-01

    A catalytic amount of tin(IV) chloride catalyzed formal [4+2] cycloaddition reaction of di-tert-butyl 2-ethoxycyclobutane-1,1-carboxylate with ketones or aldehydes to give diethyl 6-ethoxydihydro-2H-pyran-3,3(4H)-dicarboxylates, whereas two equivalents of trimethylsilyl triflate promoted tandem [4+2] cycloaddition and lactonization to afford 3-oxo-2,6-dioxabicyclo[2.2.2]octane-4-carboxylate esters. PMID:22223370

  14. Formal [4+2] Cycloaddition of di-tert-Butyl 2-Ethoxycyclobutane-1,1-dicarboxylate with Ketones or Aldehydes and Tandem Lactonization

    OpenAIRE

    Okado, Ryohei; Nowaki, Aya; Matsuo, Jun-ichi; Ishibashi, Hiroyuki

    2012-01-01

    A catalytic amount of tin(IV) chloride catalyzed formal [4+2] cycloaddition reaction of di-tert-butyl 2-ethoxycyclobutane-1,1-carboxylate with ketones or aldehydes to give diethyl 6-ethoxydihydro-2H-pyran-3,3(4H)-dicarboxylates, whereas two equivalents of trimethylsilyl triflate promoted tandem [4+2] cycloaddition and lactonization to afford 3-oxo-2,6-dioxabicyclo[2.2.2]octane-4-carboxylate esters.

  15. Threshold photoelectron spectroscopy and photoionization total ion yield spectroscopy of simple organic acids, aldehydes, ketones and amines

    International Nuclear Information System (INIS)

    We have initiated a research program to investigate the ionization behavior of some simple organic molecules containing the carboxyl group (R2C=O), where R could be H, OH, NH2, or CH3 or other aliphatic or aromatic carbon groups, using threshold photoelectron spectroscopy and photoionization total ion yield spectroscopy. We report here on the simplest organic acid, formic acid, and two simple aldehydes: acetaldehyde and the simplest unsaturated aldehyde, 2-propenal (acrolein). The objective of this study was to characterize the valence cationic states of these molecules with vibrational structural resolution.

  16. Identification and characterization of an antennae-specific aldehyde oxidase from the navel orangeworm.

    Directory of Open Access Journals (Sweden)

    Young-Moo Choo

    Full Text Available Antennae-specific odorant-degrading enzymes (ODEs are postulated to inactivate odorant molecules after they convey their signal. Different classes of insect ODEs are specific to esters, alcohols, and aldehydes--the major functional groups of female-produced, hydrophobic sex pheromones from moth species. Esterases that rapidly inactive acetate and other esters have been well-studied, but less is known about aldehyde oxidases (AOXs. Here we report cloning of an aldehyde oxidase, AtraAOX2, from the antennae of the navel orangeworm (NOW, Amyelois transitella, and the first activity characterization of a recombinant insect AOX. AtraAOX2 gene spans 3,813 bp and encodes a protein with 1,270 amino acid residues. AtraAOX2 cDNA was expressed in baculovirus-infected insect Sf21 cells as a ≈280 kDa homodimer with 140 kDa subunits. Recombinant AtraAOX2 degraded Z11Z13-16Ald and plant volatile aldehydes as substrates. However, as expected for aldehyde oxidases, recombinant AtraAOX2 did not show specificity for Z11Z13-16Ald, the main constituent of the sex pheromone, but showed high activity for plant volatile aldehydes. Our data suggest AtraAOX2 might be involved in degradation of a diversity of aldehydes including sex pheromones, plant-derived semiochemicals, and chemical cues for oviposition sites. Additionally, AtraAOX2 could protect the insect's olfactory system from xenobiotics, including pesticides that might reach the sensillar lymph surrounding the olfactory receptor neurons.

  17. Biotin Carboxyl Carrier Protein in Barley Chloroplast Membranes

    DEFF Research Database (Denmark)

    Kannangara, C. G.; Jense, C J

    1975-01-01

    Biotin localized in barley chloroplast lamellae is covalently bound to a single protein with an approximate molecular weight of 21000. It contains one mole of biotin per mole of protein and functions as a carboxyl carrier in the acetyl-CoA carboxylase reaction. The protein was obtained by...... solubilization of the lamellae in phenol/acetic acid/8 M urea. Feeding barley seedlings with [14C]-biotin revealed that the vitamin is not degraded into respiratory substrates by the plant, but is specifically incorporated into biotin carboxyl carrier protein....

  18. EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF); Scientific Opinion on Flavouring Group Evaluation 10, Revision 3 (FGE.10Rev3): Aliphatic primary and secondary saturated and unsaturated alcohols, aldehydes, acetals, carboxylic acids and esters containing an

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister; Lund, Pia; Binderup, Mona-Lise; Frandsen, Henrik Lauritz

    The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to evaluate 63 flavouring substances in the Flavouring Group Evaluation 10, including additional two substances in this Revision 3, using the Procedure in Commission R...

  19. EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF); Scientific Opinion on Flavouring Group Evaluation 10, Revision 2 (FGE.10Rev2): Aliphatic primary and secondary saturated and unsaturated alcohols, aldehydes, acetals, carboxylic acids and esters containing an

    DEFF Research Database (Denmark)

    Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister; Lund, Pia; Binderup, Mona-Lise; Frandsen, Henrik Lauritz

    The Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids of the European Food Safety Authority was requested to evaluate 61 flavouring substances in the Flavouring Group Evaluation 10, Revision 2, using the Procedure in Commission Regulation (EC) No 1565/2000. None of the sub...

  20. rac-Methyl (3aR*,4S*,5R*,7aR*)-5,7a-bis­(acet­yloxy)-3-oxo-2-phenyl­octa­hydro-1H-iso­indole-4-carboxyl­ate

    OpenAIRE

    Toze, Flavien A. A.; Nikitina, Eugeniya V.; Vladimir P. Zaytsev; Zubkov, Fedor I.; Victor N. Khrustalev

    2013-01-01

    The title molecule, C20H23NO7, the product of nucleophilic cleavage of the 3a,6-epoxy bridge in 1-oxo-2-phenyloctahydro-3a,6-epoxyisoindole-7-carboxylate, comprises a cis-fused bicyclic system containing a 2-pyrrolidinone ring in an envelope conformation (with the C atom bearing the carboxylate substituent as the flap) and a cyclohexane ring in a chair conformation. The carboxylate substituent occupies the equatorial position, whereas the two acetyloxy substituents are in axial positions. The...

  1. TEMPO-catalyzed aerobic oxidation of alcohols to aldehydes and ketones in ionic liquid [bmim][PF6].

    Science.gov (United States)

    Ansari, Imtiaz A; Gree, Rene

    2002-05-01

    [reaction: see text]. A simple and mild TEMPO-CuCl catalyzed aerobic oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones in ionic liquid [bmim][PF6] with no trace of overoxidation to carboxylic acids has been developed. The product can be isolated by a simple extraction with organic solvent, and the ionic liquid can be recycled or reused. PMID:11975615

  2. Efficient and Highly Aldehyde Selective Wacker Oxidation

    KAUST Repository

    Teo, Peili

    2012-07-06

    A method for efficient and aldehyde-selective Wacker oxidation of aryl-substituted olefins using PdCl 2(MeCN) 2, 1,4-benzoquinone, and t-BuOH in air is described. Up to a 96% yield of aldehyde can be obtained, and up to 99% selectivity can be achieved with styrene-related substrates. © 2012 American Chemical Society.

  3. Multiple aldehyde reductases of human brain.

    Science.gov (United States)

    Hoffman, P L; Wermuth, B; von Wartburg, J P

    1980-01-01

    Human brain contains four forms of aldehyde reducing enzymes. One major activity, designated AR3, has properties indicating its identity with the NADPH-dependent aldehyde reductase, EC 1.1.1.2. The other major form of human brain enzyme, AR1, which is also NADPH-dependent, reduces both aldehyde and ketone-containing substrates, including vitamin K3 (menadione) and daunorubicin, a cancer chemotherapeutic agent. This enzyme is very sensitive to inhibition by the flavonoids quercitrin and quercetine, and may be analogous to a daunorubicin reductase previously described in liver of other species. One minor form of human brain aldehyde reductase, AR2, demonstrates substrate specificity and inhibitor sensitivity which suggest its similarity to aldose reductases found in lens and other tissues of many species. This enzyme, which can also use NADH as cofactor to some extent, is the most active in reducing the aldehyde derivatives of the biogenic amines. The fourth human brain enzyme ("SSA reductase") differs from the other forms in its ability to use NADH as well as or better than NADPH as cofactor, and in its molecular weight, which is nearly twice that of the other forms. It is quite specific for succinic semialdehyde (SSA) as substrate, and was found to be significantly inhibited only by quercetine and quercitrin. AR3 can also reduce SSA, and both enzymes may contribute to the production of gamma-hydroxybutyric acid in vivo. These results indicate that the human brain aldehyde reductases can play relatively specific physiologic roles. PMID:7424738

  4. Acetate causes alcohol hangover headache in rats.

    Directory of Open Access Journals (Sweden)

    Christina R Maxwell

    Full Text Available BACKGROUND: The mechanism of veisalgia cephalgia or hangover headache is unknown. Despite a lack of mechanistic studies, there are a number of theories positing congeners, dehydration, or the ethanol metabolite acetaldehyde as causes of hangover headache. METHODS: We used a chronic headache model to examine how pure ethanol produces increased sensitivity for nociceptive behaviors in normally hydrated rats. RESULTS: Ethanol initially decreased sensitivity to mechanical stimuli on the face (analgesia, followed 4 to 6 hours later by inflammatory pain. Inhibiting alcohol dehydrogenase extended the analgesia whereas inhibiting aldehyde dehydrogenase decreased analgesia. Neither treatment had nociceptive effects. Direct administration of acetate increased nociceptive behaviors suggesting that acetate, not acetaldehyde, accumulation results in hangover-like hypersensitivity in our model. Since adenosine accumulation is a result of acetate formation, we administered an adenosine antagonist that blocked hypersensitivity. DISCUSSION: Our study shows that acetate contributes to hangover headache. These findings provide insight into the mechanism of hangover headache and the mechanism of headache induction.

  5. Overview on mechanisms of acetic acid resistance in acetic acid bacteria.

    Science.gov (United States)

    Wang, Bin; Shao, Yanchun; Chen, Fusheng

    2015-02-01

    Acetic acid bacteria (AAB) are a group of gram-negative or gram-variable bacteria which possess an obligate aerobic property with oxygen as the terminal electron acceptor, meanwhile transform ethanol and sugar to corresponding aldehydes, ketones and organic acids. Since the first genus Acetobacter of AAB was established in 1898, 16 AAB genera have been recorded so far. As the main producer of a world-wide condiment, vinegar, AAB have evolved an elegant adaptive system that enables them to survive and produce a high concentration of acetic acid. Some researches and reviews focused on mechanisms of acid resistance in enteric bacteria and made the mechanisms thoroughly understood, while a few investigations did in AAB. As the related technologies with proteome, transcriptome and genome were rapidly developed and applied to AAB research, some plausible mechanisms conferring acetic acid resistance in some AAB strains have been published. In this review, the related mechanisms of AAB against acetic acid with acetic acid assimilation, transportation systems, cell morphology and membrane compositions, adaptation response, and fermentation conditions will be described. Finally, a framework for future research for anti-acid AAB will be provided. PMID:25575804

  6. Ion exchange properties of carboxylate bagasse

    International Nuclear Information System (INIS)

    Bagasse fibers were chemically modified using three different reactions: esterification using monochloro acetic acid, esterification using succinic anhydride, and oxidation using sodium periodate and sodium chlorite to prepare cation exchanger bearing carboxylic groups. Bagasse was crosslinked using epichlorohydrin before chemical modification to avoid loss of its constituents during the chemical modification. The structure of the prepared derivatives was proved using Fourier transform infrared (FTIR) and chemical methods. The ability of the prepared bagasse cation exchangers to adsorb heavy metal ions (Cu+2, Ni+2, Cr+3, Fe+3), on a separate basis or in a mixture of them, at different metal ion concentration was tested. Thermal stability of the different bagasse derivative was studied using thermogravimetric analysis (TGA)

  7. Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes

    International Nuclear Information System (INIS)

    Tris-carboxylate complexes of the uranyl (UO2)2+ cation with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transformion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetatouranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric -CO2 stretches of both the monodentate and bidentate acetate, CH3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate, and two bidentate benzoate ligands.

  8. Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Groenewold, G. S.; De Jong, Wibe A.; Oomens, Jos; Van Stipdonk, Michael J.

    2010-05-01

    Tris-carboxylate complexes of the uranyl [UO2]2+ cation with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transformion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetatouranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric -CO2 stretches of both the monodentate and bidentate acetate, CH3 bending and umbrella vibrations, and a uranyl O-U-O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate, and two bidentate benzoate ligands.

  9. Evans-Tishchenko coupling of heteroaryl aldehydes.

    Science.gov (United States)

    Dorgan, Philip D; Durrani, Jamie; Cases-Thomas, Manuel J; Hulme, Alison N

    2010-11-01

    The low-temperature Evans-Tishchenko coupling of a range of functionalized heteroaryl aldehydes with β-hydroxy ketones in the presence of a Sm(III) catalyst has been achieved with high yields (90-99%) and good to excellent diastereoselectivity (90:10 → 95:5 dr). However, at room temperature a retro-aldol aldol-Tishchenko reaction was found to compete with the desired Evans-Tishchenko reaction. Identification of these byproducts has allowed the corresponding aldol-Tishchenko reaction to be optimized for several heteroaryl aldehydes. PMID:20929205

  10. Aldehyde dehydrogenase protein superfamily in maize.

    Science.gov (United States)

    Zhou, Mei-Liang; Zhang, Qian; Zhou, Ming; Qi, Lei-Peng; Yang, Xiong-Bang; Zhang, Kai-Xuan; Pang, Jun-Feng; Zhu, Xue-Mei; Shao, Ji-Rong; Tang, Yi-Xiong; Wu, Yan-Min

    2012-11-01

    Maize (Zea mays ssp. mays L.) is an important model organism for fundamental research in the agro-biotechnology field. Aldehydes were generated in response to a suite of environmental stresses that perturb metabolism including salinity, dehydration, desiccation, and cold and heat shock. Many biologically important aldehydes are metabolized by the superfamily of NAD(P)(+)-dependent aldehyde dehydrogenases. Here, starting from the database of Z. mays, we identified 28 aldehyde dehydrogenase (ALDH) genes and 48 transcripts by the in silico cloning method using the ALDH-conserved domain amino acid sequence of Arabidopsis and rice as a probe. Phylogenetic analysis shows that all 28 members of the ALDH gene families were classified to ten distinct subfamilies. Microarray data and quantitative real-time PCR analysis reveal that ZmALDH9, ZmALDH13, and ZmALDH17 genes involve the function of drought stress, acid tolerance, and pathogens infection. These results suggested that these three ZmALDH genes might be potentially useful in maize genetic improvement. PMID:22983498

  11. Tricarbonylchrom-Komplexe aromatischer Aldehyde und Ketone

    OpenAIRE

    Effenberger, Franz; Schöllkopf, Klaus

    1985-01-01

    Tricarbonylchrom (TCC)-Komplexe 2, 3 aromatischer Aldehyde und Ketone werden einmal durch basekatalysierte Carbodesilylierung von TCC-Aryltrimethylsilan-Komplexen 1 mit Dime-thylformamid bzw. Benzoylfluorid, zum anderen durch selektive Oxidation von TCC-Phenyl-methanol-Komplexen 5 mit speziell präpariertem Mangandioxid in Ether dargestellt.

  12. 40 CFR 721.5762 - Aromatic aldehyde phenolic resin (generic).

    Science.gov (United States)

    2010-07-01

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

  13. 1-Azaniumylcyclobutane-1-carboxylate monohydrate

    Directory of Open Access Journals (Sweden)

    Ray J. Butcher

    2014-02-01

    Full Text Available In the title compound, C5H9NO2·H2O, the amino acid is in the usual zwitterionic form involving the α-carboxylate group. The cyclobutane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7 and 0.118 (7. In the crystal, N—H...O and O—H...O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3+ and donor (through a single carboxylate O from two different aminocyclobutane carboxylate moities], resulting in a two-dimensional layered structure lying parallel to (100.

  14. Enhanced dispersion stability and mobility of carboxyl-functionalized carbon nanotubes in aqueous solutions through strong hydrogen bonds

    International Nuclear Information System (INIS)

    Dispersion of carbon nanotubes has been heavily studied due to its importance for their technical applications, toxic effects, and environmental impacts. Common electrolytes, such as sodium chloride and potassium chloride, promote agglomeration of nanoparticles in aqueous solutions. On the contrary, we discovered that acetic electrolytes enhanced the dispersion of multi-walled carbon nanotubes (MWCNTs) with carboxyl functional group through the strong hydrogen bond, which was confirmed by UV–Vis spectrometry, dispersion observations and aerosolization-quantification method. When concentrations of acetate electrolytes such as ammonium acetate (CH3CO2NH4) and sodium acetate (CH3CO2Na) were lower than 0.03 mol per liter, MWCNT suspensions showed better dispersion and had higher mobility in porous media. The effects by the acetic environment are also applicable to other nanoparticles with the carboxyl functional group, which was demonstrated with polystyrene latex particles as an example

  15. Enhanced dispersion stability and mobility of carboxyl-functionalized carbon nanotubes in aqueous solutions through strong hydrogen bonds

    Energy Technology Data Exchange (ETDEWEB)

    Bahk, Yeon Kyoung; He, Xu; Gitsis, Emmanouil; Kuo, Yu-Ying [ETH Zurich, Institute of Environmental Engineering (Switzerland); Kim, Nayoung [EMPA, Building Energy Materials and Components (Switzerland); Wang, Jing, E-mail: jing.wang@ifu.baug.ethz.ch [ETH Zurich, Institute of Environmental Engineering (Switzerland)

    2015-10-15

    Dispersion of carbon nanotubes has been heavily studied due to its importance for their technical applications, toxic effects, and environmental impacts. Common electrolytes, such as sodium chloride and potassium chloride, promote agglomeration of nanoparticles in aqueous solutions. On the contrary, we discovered that acetic electrolytes enhanced the dispersion of multi-walled carbon nanotubes (MWCNTs) with carboxyl functional group through the strong hydrogen bond, which was confirmed by UV–Vis spectrometry, dispersion observations and aerosolization-quantification method. When concentrations of acetate electrolytes such as ammonium acetate (CH{sub 3}CO{sub 2}NH{sub 4}) and sodium acetate (CH{sub 3}CO{sub 2}Na) were lower than 0.03 mol per liter, MWCNT suspensions showed better dispersion and had higher mobility in porous media. The effects by the acetic environment are also applicable to other nanoparticles with the carboxyl functional group, which was demonstrated with polystyrene latex particles as an example.

  16. Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

    Science.gov (United States)

    Vaïtilingom, M.; Charbouillot, T.; Deguillaume, L.; Maisonobe, R.; Parazols, M.; Amato, P.; Sancelme, M.; Delort, A.-M.

    2011-02-01

    Clouds are multiphasic atmospheric systems in which the dissolved organic compounds, dominated by carboxylic acids, are subject to multiple chemical transformations in the aqueous phase. Among them, solar radiation, by generating hydroxyl radicals (•OH), is considered as the main catalyzer of the reactivity of organic species in clouds. We investigated to which extent the active biomass existing in cloud water represents an alternative route to the chemical reactivity of carboxylic acids. Pure cultures of seventeen bacterial strains (Arthrobacter, Bacillus, Clavibacter, Frigoribacterium, Pseudomonas, Sphingomonas and Rhodococcus), previously isolated from cloud water and representative of the viable community of clouds were first individually incubated in two artificial bulk cloud water solutions at 17 °C and 5 °C. These solutions mimicked the chemical composition of cloud water from "marine" and "continental" air masses, and contained the major carboxylic acids existing in the cloud water (i.e. acetate, formate, succinate and oxalate). The concentrations of these carboxylic compounds were monitored over time and biodegradation rates were determined. In average, they ranged from 2 ×10-19 for succinate to 1 × 10-18 mol cell-1 s-1 for formate at 17 °C and from 4 × 10-20 for succinate to 6 × 10-19 mol cell-1 s-1 for formate at 5 °C, with no significant difference between "marine" and "continental" media. In parallel, irradiation experiments were also conducted in these two artificial media to compare biodegradation and photodegradation of carboxylic compounds. To complete this comparison, the photodegradation rates of carboxylic acids by •OH radicals were calculated from literature data. Inferred estimations suggested a significant participation of microbes to the transformation of carboxylic acids in cloud water, particularly for acetate and succinate (up to 90%). Furthermore, a natural cloud water sample was incubated (including its indigenous microflora

  17. Chemistry and electrochemistry in trifluoroacetic acid. Comparison with acetic acid

    International Nuclear Information System (INIS)

    As the trifluoroacetic acid is, with the acetic acid, one of most often used carboxylic acids as solvent, notably in organic chemistry, this research thesis addresses some relatively simple complexing and redox reactions to highlight the peculiar feature of this acid, and to explain its very much different behaviour with respect to acetic acid. The author develops the notion of acidity level in solvents of low dielectric constant. The second part addresses a specific solvent: BF3(CH3COOH)2. The boron trifluoride strengthens the acidity of acetic acid and modifies its chemical and physical-chemical properties. In the third part, the author compares solvent properties of CF3COOH and CH3COOH. Noticed differences explain why the trifluoroacetic acid is a more interesting reaction environment than acetic acid for reactions such as electrophilic substitutions or protein solubilisation

  18. Deodorants: an experimental provocation study with cinnamic aldehyde

    DEFF Research Database (Denmark)

    Bruze, Magnus; Johansen, Jeanne Duus; Andersen, Klaus Ejner; Frosch, P; Lepoittevin, J-P; Rastogi, S; Wakelin, S; White, I; Menné, T

    2003-01-01

    of axillary dermatitis when used by individuals with and without contact allergy to cinnamic aldehyde. METHODS: Patch tests with deodorants and ethanol solutions with cinnamic aldehyde, and repeated open application tests with roll-on deodorants without and with cinnamic aldehyde at different...... concentrations, were performed in 37 patients with dermatitis, 20 without and 17 with contact allergy to cinnamic aldehyde. RESULTS: A repeated open application test with positive findings was noted only in patients hypersensitive to cinnamic aldehyde (P <.001) and only in the axilla to which the deodorants...

  19. Abscisic (ABA)-aldehyde is a precursor to, and 1',4'-trans-ABA-diol a catabolite of, ABA in apple

    International Nuclear Information System (INIS)

    Previous 18O labeling studies of abscisic acid (ABA) have shown that apple (Malus domestica Borkh. cv Granny Smith) fruits synthesize a majority of [18O]ABA with the label incorporated in the 1'-hydroxyl position and unlabeled in the carboxyl group (JAD Zeevaart, TG Heath, DA Gage [1989] Plant Physiol 91: 1594-1601). It was proposed that exchange of 18O in the side chain with the medium occurred at an aldehyde intermediate stage of ABA biosynthesis. We have isolated ABA-aldehyde and 1'-4'-trans-ABA-diol (ABA-trans-diol) from 18O-labeled apple fruit tissue and measured the extent and position of 18O incorporation by tandem mass spectrometry. 18O-Labeling patterns of ABA-aldehyde, ABA-trans-diol, and ABA indicate that ABA-aldehyde is a precursor to, and ABA-trans-diol a catabolite of, ABA. Exchange of 18O in the carbonyl of ABA-aldehyde can be the cause of loss of 18O from the side chain of [18O]ABA. Results of feeding experiments with deuterated substrates provide further support for the precursor-product relationship of ABA-aldehyde → ABA → ABA-trans-diol. The ABA-aldehyde and ABA-trans-diol contents of fruits and leaves were low, approximately 1 and 0.02 nanograms per gram fresh weight for ABA-aldehyde and ABA-trans-diol, respectively, while ABA levels in fruits ranged from 10 to 200 nanograms per gram fresh weight. ABA biosynthesis was about 10-fold lower in fruits than in leaves. In fruits, the majority of ABA was conjugated to β-D-glucopyranosyl abscisate, whereas in leaves ABA was mainly hydroxylated to phaseic acid. Parallel pathways for ABA and trans-ABA biosynthesis and conjugation in fruits and leaves are proposed

  20. Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

    KAUST Repository

    Zhang, Tao

    2014-01-01

    Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation. It is unknown whether this process is effective for all carboxylates or selective to special molecule structures. In this work, the selectivity was confirmed using O3/(CuO/CeO2) and six distinct ozone-resistant probe carboxylates (i.e., acetate, citrate, malonate, oxalate, pyruvate and succinate). Among these probe compounds, pyruvate, oxalate, and citrate were readily degraded following the rate order of oxalate>citrate>pyruvate, while the degradation of acetate, malonate, and succinate was not promoted. The selectivity was independent on carboxylate group number of the probe compounds and solution pH. Competitive degradation was observed for carboxylate mixtures following the preference order of citrate, oxalate, and finally pyruvate. The competitive degradation was ascribed to competitive adsorption on the catalyst surface. It was revealed that the catalytically degradable compounds formed bidentate chelating or bridging complexes with surface copper sites of the catalyst, i.e., the active sites. The catalytically undegradable carboxylates formed monodentate complexes with surface copper sites or just electrostatically adsorbed on the catalyst surface. The selectivity, relying on the structure of surface metal-carboxylate complex, should be considered in the design of catalytic ozonation process. © 2013 Elsevier B.V.

  1. Development of an automated modular system for the synthesis of [11C]acetate

    DEFF Research Database (Denmark)

    Felicini, Chiara; Någren, Kjell; Berton, Andrea; Pascali, Giancarlo; Salvadori, Piero Alberto

    2010-01-01

    Carboxylation reactions offer a straightforward method for the synthesis of carbon-11 labelled carboxylic acids. Among these, the preparation of carbon-11 (C)-acetate is receiving increasing attention because of diagnostic applications in oncology in addition to its well-established use as a prob...... for myocardial oxidative metabolism. Although a number of dedicated modules are commercially available, the development of the synthesis on flexible platforms would be beneficial to widen the number of tracers, in particular for preclinical assessment and testing....

  2. Carboxylic acid reductase is a versatile enzyme for the conversion of fatty acids into fuels and chemical commodities

    OpenAIRE

    Akhtar, M. K.; Turner, N. J.; Jones, P R

    2012-01-01

    Aliphatic hydrocarbons such as fatty alcohols and petroleum-derived alkanes have numerous applications in the chemical industry. In recent years, the renewable synthesis of aliphatic hydrocarbons has been made possible by engineering microbes to overaccumulate fatty acids. However, to generate end products with the desired physicochemical properties (e.g., fatty aldehydes, alkanes, and alcohols), further conversion of the fatty acid is necessary. A carboxylic acid reductase (CAR) from Mycobac...

  3. Acetate and CO2 assimilation by Methanothrix concilii.

    OpenAIRE

    Ekiel, I; Sprott, G D; Patel, G. B.

    1985-01-01

    Biosynthetic pathways in Methanothrix concilii, a recently isolated aceticlastic methanogen, were studied by 13C-nuclear magnetic resonance spectroscopy. Labeling patterns of amino acids, lipids, and carbohydrates were determined. Similar to other methanogens, acetate was carboxylated to pyruvate, which was further converted to amino acids by various biosynthetic pathways. The origin of carbon atoms in glutamate, proline, and arginine clearly showed that an incomplete tricarboxylic acid cycle...

  4. Separation and determination of some carboxylic acids by capillary electrophoresis

    Energy Technology Data Exchange (ETDEWEB)

    Sladkov, V.; Fourest, B

    2006-07-01

    Separation and determination of some organic acids, mono-carboxylic (formic and acetic), dicarboxylic (oxalic and tartaric), tricarboxylic (citric) acids and aromatic acids (phtalic, benzoic, mellitic and trimellitic), by capillary electrophoresis are reviewed. The method development parameters, such as separation and injection mode, are discussed. Special attention is paid to the comparison of different detection types (spectroscopic and electrochemical). The optimisation of the carrier electrolyte composition (choice of carrier electrolyte, effect of pH, ionic strength, electro-osmotic flow modifier) is treated. Different additives (alkali-earth and transition metal ions, cyclodextrins and alcohol), which are often used for improving organic acid separation, are also considered. (authors)

  5. Separation and determination of some carboxylic acids by capillary electrophoresis

    International Nuclear Information System (INIS)

    Separation and determination of some organic acids, mono-carboxylic (formic and acetic), dicarboxylic (oxalic and tartaric), tricarboxylic (citric) acids and aromatic acids (phtalic, benzoic, mellitic and trimellitic), by capillary electrophoresis are reviewed. The method development parameters, such as separation and injection mode, are discussed. Special attention is paid to the comparison of different detection types (spectroscopic and electrochemical). The optimisation of the carrier electrolyte composition (choice of carrier electrolyte, effect of pH, ionic strength, electro-osmotic flow modifier) is treated. Different additives (alkali-earth and transition metal ions, cyclodextrins and alcohol), which are often used for improving organic acid separation, are also considered. (authors)

  6. Homogeneous catalytic hydrogenation of bio-oil and related model aldehydes with RuCl{sub 2}(PPh{sub 3}){sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Huang, F.; Li, W.; Lu, Q.; Zhu, X. [Anhui Province Key Laboratory of Biomass Clean Energy, University of Science and Technology of China, Hefei (China)

    2010-12-15

    A homogeneous RuCl{sub 2}(PPh{sub 3}){sub 3} catalyst was prepared for the hydrogenation of bio-oil to improve its stability and fuel quality. Experiments were first performed on three model aldehydes of acetaldehyde, furfural and vanillin selected to represent the linear aldehydes, oxygen heterocyclic aldehydes and aromatic aldehydes in bio-oil. The results demonstrated the high hydrogenation capability of this homogeneous catalyst under mild conditions (55-90 C, 1.3-3.3 MPa). The highest conversion of the three model aldehydes was over 90 %. Furfural and acetaldehyde were singly converted to furfuryl alcohol and ethanol after hydrogenation, while vanillin was mainly converted to vanillin alcohol, together with a small amount of 2-methoxy-4-methylphenol and 2-methoxyphenol. Further experiments were conducted on a bio-oil fraction extracted by ethyl acetate and on the whole bio-oil at 70 C and 3.3 MPa. Most of the aldehydes were transformed to the corresponding alcohols, and some ketones and compounds with C-C double bond were converted to more stable compounds. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  7. On the one pot syntheses of chromeno[4,3-b]pyridine-3-carboxylate and chromeno[3,4-c]pyridine-3-carboxylate and dihydropyridines

    Energy Technology Data Exchange (ETDEWEB)

    Navarrete-Encina, Patricio A.; Vega-Retter, Christian, E-mail: pnavarre@vtr.ne [Universidad de Chile, Santiago (Chile). Facultad de Ciencias Quimicas y Farmaceuticas. Lab. de Sintesis Organica y Fisicoquimica; Salazar, Ricardo; Perez, Karina; Squella, Juan A.; Nunez-Vergara, Luis J. [Universidad de Chile, Santiago (Chile). Fac. de Ciencias Quimicas y Farmaceuticas. Lab. de Bioelectroquimica

    2010-07-01

    Substituted chromenos, dihydropyridines and pyridines have been important in the syntheses of compounds having interesting pharmacological properties. Therefore, we found of interest to synthesize chromenopyridines and chromeno dihydropyridines (i.e., fused chromeno and dihydropyridine or pyridine rings) to further study their biological activity. Here, we propose one-pot syntheses for substituted ethyl-2,4-dimethyl-5-oxo-5H-chromeno[4,3-b]pyridine-3-carboxylates, ethyl-2,4-dimethyl-5-oxo-5H-chromeno[3,4-c]pyridine-3-carboxylates and their respective 1,4-dihydropyridines based on a modified Hantzsch pyridine synthesis using 2-hydroxyaryl aldehydes, with electron withdrawing and electron donating groups on the phenyl ring, as starting reactants. Sixteen compounds were synthesized by the described method and fully characterized. An average yield of 37% was obtained for the different derivatives. (author)

  8. Mercury(II) Acetate

    Czech Academy of Sciences Publication Activity Database

    Dejmek, Milan

    2012-01-01

    Roč. 23, č. 19 (2012), s. 2867-2868. ISSN 0936-5214 Institutional support: RVO:61388963 Keywords : mercury(II) acetate * oxymercuration Subject RIV: CC - Organic Chemistry Impact factor: 2.655, year: 2012

  9. 14CO2 ratios method for detecting pyruvate carboxylation

    International Nuclear Information System (INIS)

    The pattern of oxidative metabolism of pyruvate may be assessed by comparing the steady-state 14CO2 production from four isotopes in identical samples. The assay requires measuring the ratios of steady-state 14CO2 production from two isotope pairs, [2-14C]pyruvate:[3-14C]pyruvate and [1-14C]acetate:[2-14C]acetate. These ratios are defined as the ''pyruvate 14CO2 ratio'' and the ''acetate 14CO2 ratio,'' respectively. If pyruvate is metabolized exclusively via pyruvate dehydrogenase (PDH), the two ratios will be identical. Alternatively, if any pyruvate enters the tricarboxylic acid (TCA) cycle via pyruvate carboxylation (PC), the pyruvate 14CO2 ratio will be less than the acetate 14CO2 ratio. If pyruvate enters the TCA cycle only through PC (with oxaloacetate and fumarate in equilibrium) the pyruvate 14CO2 ratio will approach a value of 1.0. An equation is presented for the quantitative evaluation of pyruvate oxidation by these two pathways. We have used this method to detect relative changes in the pattern of pyruvate metabolism in rat liver mitochondria produced by exposure to 1 mM octanoyl carnitine, a compound known to alter the PC:PDH activity ratio. The major advantages of the method are (i) that it provides a sensitive method for detecting pyruvate carboxylation at physiological pyruvate concentrations and (ii) that it provides a method for distinguishing between effects on pyruvate transport and effects on pyruvate oxidation

  10. Carboxyl group reactivity in actin

    International Nuclear Information System (INIS)

    While earlier work showed that the carboxyl groups of proteins could be quantitatively coupled to amino groups at pH 4.75 in the presence of EDC and a denaturing agent, the work presented here indicates that under milder conditions the modification of sidechain carboxyls is limited and somewhat specific. Most of the incorporated glycine ethyl ester (GEE) is apparently bound to five carboxyls. The total GEE incorporated was 3 to 4 moles/mole of protein as measured by an increase in Gly upon acid hydrolysis and amino acid analysis, as well as total radioactivity. 3.55 residues were found in peptides, 2.75 bound to residues 1 to 4, and 0.8 bound to Gly-100. 9 refs., 2 figs., 2 tabs

  11. Chiral allyl silane additions to chiral α-substituted aldehydes

    International Nuclear Information System (INIS)

    Chiral allyl silane 3 reacted with chiral α-methyl-β-siloxy-aldehydes to afford the corresponding 1,4-syn-products with good diastereo-selectivities independent of the absolute stereochemistry of these aldehydes. The best selectivities are observed when the reactions are carried out by trans metallation of the allyl silane 3 using Tin (IV) Chloride in CH2 CL2 at -78 deg C, before addition of the aldehydes. (author)

  12. Aldehyde Dehydrogenases in Cellular Responses to Oxidative/electrophilic Stress

    OpenAIRE

    Singh, Surendra; Brocker, Chad; Koppaka, Vindhya; Ying, Chen; Jackson, Brian; Matsumoto, Akiko; Thompson, David C.; Vasiliou, Vasilis

    2012-01-01

    Reactive oxygen species (ROS) are continuously generated within living systems and the inability to manage ROS load leads to elevated oxidative stress and cell damage. Oxidative stress is coupled to the oxidative degradation of lipid membranes, also known as lipid peroxidation. This process generates over 200 types of aldehydes, many of which are highly reactive and toxic. Aldehyde dehydrogenases (ALDHs) metabolize endogenous and exogenous aldehydes and thereby mitigate oxidative/electrophili...

  13. Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Bag, Soumabha; Hendricks, P.I. [Aston Labs, Department of Chemistry, Purdue University, West Lafayette, IN 47907 (United States); Reynolds, J.C. [Centre for Analytical Science, Loughborough University, Loughborough, Leicestershire (United Kingdom); Cooks, R.G., E-mail: cooks@purdue.edu [Aston Labs, Department of Chemistry, Purdue University, West Lafayette, IN 47907 (United States)

    2015-02-20

    Highlights: • In-situ derivatization and simultaneous ionization used to detect aldehydes. • Biogenic aliphatic and aromatic aldehydes reacted with 4-aminophenol. • Derivatized products yield structurally characteristic fragment ions. • This measurement demonstrated using a miniaturized portable mass spectrometer. - Abstract: Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer.

  14. Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry

    International Nuclear Information System (INIS)

    Highlights: • In-situ derivatization and simultaneous ionization used to detect aldehydes. • Biogenic aliphatic and aromatic aldehydes reacted with 4-aminophenol. • Derivatized products yield structurally characteristic fragment ions. • This measurement demonstrated using a miniaturized portable mass spectrometer. - Abstract: Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer

  15. Cyclodextrin Aldehydes are Oxidase Mimics

    DEFF Research Database (Denmark)

    Fenger, Thomas Hauch; Bjerre, Jeannette; Bols, Mikael

    2009-01-01

    Cyclodextrins containing 6-aldehyde groups were found to catalyse oxidation of aminophenols in the presence of hydrogen peroxide. The catalysis followed Michaelis-Menten kinetics and is related to the catalysis previously observed with cyclodextrin ketones. A range of different cyclodextrin...... aldehydes were prepared containing one, two or more aldehydes at the primary rim (6-positions) or a ethoxy-2-al or propoxy-3-al at the secondary rim. 2-O-ethoxy-2-al- -cyclodextrin was found to be the best catalyst. The aldehydes are in many cases better catalysts than the ketones, because of their powerful...

  16. Dissimilation of carbon monoxide to acetic acid by glucose-limited cultures of Clostridium thermoaceticum

    International Nuclear Information System (INIS)

    Clostridium thermoaceticum was cultivated in glucose-limited media, and the dissimilation of CO to acetic acid was evaluated. The authors found that cultures catalyzed the rapid dissimilation of CO to acetic acid and CO2, with the stoichiometry obtained for conversion approximating that predicted from the following reaction: 4CO + 2H2O → CH3CO2H + 2CO2. Growing cultures formed approximately 50 mmol (3 g) of CO-derived acetic acid per liter of culture, with the rate of maximal consumption approximating 9.1 mmol of CO consumed/h per liter of culture. In contrast, resting cells were found not to dissimilate CO to acetic acid. 14CO was incorporated, with equal distribution between the carboxyl and methyl carbons of acetic acid when the initial cultivation gas phase was 100% CO whereas 14CO2 preferentially entered the carboxyl carbon when the initial gas phase was 100% CO2. Significantly, in the presence of saturating levels of CO, 14CO2 preferentially entered the methyl carbon, whereas saturating levels of CO2 yielded 14CO-derived labeling predominantly in the carboxyl carbon. These findings are discussed in relation to the path of carbon flow to acetic acid

  17. A coniferyl aldehyde dehydrogenase gene from Pseudomonas sp. strain HR199 enhances the conversion of coniferyl aldehyde by Saccharomyces cerevisiae.

    Science.gov (United States)

    Adeboye, Peter Temitope; Olsson, Lisbeth; Bettiga, Maurizio

    2016-07-01

    The conversion of coniferyl aldehyde to cinnamic acids by Saccharomyces cerevisiae under aerobic growth conditions was previously observed. Bacteria such as Pseudomonas have been shown to harbor specialized enzymes for converting coniferyl aldehyde but no comparable enzymes have been identified in S. cerevisiae. CALDH from Pseudomonas was expressed in S. cerevisiae. An acetaldehyde dehydrogenase (Ald5) was also hypothesized to be actively involved in the conversion of coniferyl aldehyde under aerobic growth conditions in S. cerevisiae. In a second S. cerevisiae strain, the acetaldehyde dehydrogenase (ALD5) was deleted. A prototrophic control strain was also engineered. The engineered S. cerevisiae strains were cultivated in the presence of 1.1mM coniferyl aldehyde under aerobic condition in bioreactors. The results confirmed that expression of CALDH increased endogenous conversion of coniferyl aldehyde in S. cerevisiae and ALD5 is actively involved with the conversion of coniferyl aldehyde in S. cerevisiae. PMID:27070284

  18. Structural Studies of the Serine-Carboxyl Proteinase Kumamolisin and the Metallopeptidase Peptidyl-Dipeptidase Dcp

    OpenAIRE

    Comellas Bigler, Mireia

    2007-01-01

    The crystal structure of the serine-carboxyl proteinase kumamolisin was solved in native form and in complex with two aldehyde inhibitors. The structures show a subtilisin-like fold with a modified catalytic triad (Ser-Glu-Asp), which allows proteolytic activity at acidic pH. The crystal structure analysis of the full-length prokumamolisin S278A exhibits an uncleaved linker segment that extends along the active-site cleft in a substrate-like manner. This evidence points to an autocatalytic cl...

  19. Crystal structure of febuxostat–acetic acid (1/1

    Directory of Open Access Journals (Sweden)

    Min Wu

    2015-05-01

    Full Text Available The asymmetric unit of the title compound [systematic name: 2-(3-cyano-4-isobutyloxyphenyl-4-methylthiazole-5-carboxylic acid–acetic acid (1/1], C16H16N2O3S·CH3COOH, contains a febuxostat molecule and an acetic acid molecule. In the febuxostat molecule, the thiazole ring is nearly coplanar with the benzene ring [dihedral angle = 3.24 (2°]. In the crystal, the febuxostat and acetic acid molecules are linked by O—H...O, O—H...N hydrogen bonds and weak C—H...O hydrogen bonds, forming supramolecular chains propagating along the b-axis direction. π–π stacking is observed between nearly parallel thiazole and benzene rings of adjacent molecules; the centroid-to-centroid distances are 3.8064 (17 and 3.9296 (17 Å.

  20. Synthesis and Characterization of Manganese Carboxylates

    OpenAIRE

    Maryudi; R.M. Yunus; A.H. Nour; M.H. Abidin

    2009-01-01

    The explorations of prodegradant additives for plastics from trans-metals organic salts have been being conducted. This study reports a method of synthesis of manganese carboxylates and their characterization. The new method involves reaction between molten carboxylic acid with sodium hydroxide in alcoholic solution to produce sodium carboxylate and continued by reacting sodium carboxylate with chloride salt of manganese. First reaction and second reaction were conducted at 80-85°C and under ...

  1. Olfactory responses of blowflies to aliphatic aldehydes.

    Science.gov (United States)

    DETHIER, V G

    1954-07-20

    The response of the blowfly Phormia regina to stimulation by aldehydes in the vapor phase has been studied by means of a specially designed olfactometer. The median rejection threshold and the maximum acceptance threshold were selected as criteria of response. For both acceptance and rejection the distribution of thresholds in the population is normal with respect to the logarithm of concentration. When thresholds are expressed as molar concentrations, the values decrease progressively as chain length is increased. There is no attraction beyond decanal and no rejection beyond dodecanal. When thresholds are expressed as activities, most members of the aldehyde series are approximately equally stimulating at rejection and equally stimulating at acceptance. The relationship is most exact over the middle range of chain lengths. There is a tendency for the terminal members to stimulate at higher activities. These relationships are in close agreement with those which were found earlier to apply to the normal aliphatic alcohols. The similarity between the relative actions of the members of the two series suggests that the relation of equal olfactory stimulation at equal thermodynamic activities by homologous aliphatic compounds at least for homologues of intermediate chain length may be of rather general application in olfaction. PMID:13174780

  2. Supported -pyrrolidine-2-carboxylic acid-4-hydrogen sulphate on silica gel as an economical and efficient catalyst for the one-pot preparation of -acetamido ketones via a four-component condensation reaction

    Indian Academy of Sciences (India)

    Arash Ghorbani-Choghamarani; Parisa Zamani

    2014-01-01

    An efficient, one-pot, four-component condensation of aldehydes, acetophenone (or propiophenone), acetyl chloride and acetonitrile in the presence of catalytic amounts of -pyrrolidine-2-carboxylic acid-4-hydrogen sulphate (supported on silica gel), a green and non-toxic catalyst, is described for the preparation of -acetamido ketones in good to excellent yields.

  3. The oxidation of the aldehyde groups in dialdehyde starch

    NARCIS (Netherlands)

    Haaksman, I.K.; Besemer, A.C.; Jetten, J.M.; Timmermans, J.W.; Slaghek, T.M.

    2006-01-01

    This paper describes the difference in relative reactivity of the aldehyde groups present in dialdehyde starch towards different oxidising agents. The oxidation of dialdehyde starch with peracetic acid and sodium bromide leads to only partial oxidation to give mono-aldehyde-carboxy starch, while oxi

  4. Adamantane-1-ammonium acetate

    Directory of Open Access Journals (Sweden)

    Elise J. C. de Vries

    2011-06-01

    Full Text Available In the title compound, C10H18N+·C2H3O2−, the ammonium H atoms of the cation are linked to three acetate anions via N—H...O hydrogen bonds, forming a chain structure extending along the b axis.

  5. Asymmetric α,γ-Regioselective [3 + 3] Formal Cycloadditions of α,β-Unsaturated Aldehydes via Cascade Dienamine-Dienamine Catalysis.

    Science.gov (United States)

    Xiao, Wei; Yin, Xiang; Zhou, Zhi; Du, Wei; Chen, Ying-Chun

    2016-01-01

    Asymmetric α,γ-regioselective [3 + 3] formal cycloadditions of α,β-unsaturated aldehydes and 2-nitroallylic acetates have been developed for the first time. These reactions proceeded through a domino Michael addition-Michael addition sequence via an unusual cascade dienamine-dienamine catalysis of a chiral secondary amine, and multifunctional cyclohexene derivatives were generally constructed in moderate yields with excellent stereoselectivity after simple treatment with K2CO3. PMID:26653774

  6. The Oxidative Fermentation of Ethanol in Gluconacetobacter diazotrophicus Is a Two-Step Pathway Catalyzed by a Single Enzyme: Alcohol-Aldehyde Dehydrogenase (ADHa)

    OpenAIRE

    Saúl Gómez-Manzo; José E. Escamilla; Abigail González-Valdez; Gabriel López-Velázquez; América Vanoye-Carlo; Jaime Marcial-Quino; Ignacio de la Mora-de la Mora; Itzhel Garcia-Torres; Sergio Enríquez-Flores; Martha Lucinda Contreras-Zentella; Roberto Arreguín-Espinosa; Kroneck, Peter M H; Martha Elena Sosa-Torres

    2015-01-01

    Gluconacetobacter diazotrophicus is a N2-fixing bacterium endophyte from sugar cane. The oxidation of ethanol to acetic acid of this organism takes place in the periplasmic space, and this reaction is catalyzed by two membrane-bound enzymes complexes: the alcohol dehydrogenase (ADH) and the aldehyde dehydrogenase (ALDH). We present strong evidence showing that the well-known membrane-bound Alcohol dehydrogenase (ADHa) of Ga. diazotrophicus is indeed a double function enzyme, which is able to ...

  7. Low-molecular-weight carboxylic acids produced from hydrothermal treatment of organic wastes.

    Science.gov (United States)

    Quitain, Armando T; Faisal, Muhammad; Kang, Kilyoon; Daimon, Hiroyuki; Fujie, Koichi

    2002-07-22

    This article reports production of low-molecular-weight carboxylic acids from the hydrothermal treatment of representative organic wastes and compounds (i.e. domestic sludge, proteinaceous, cellulosic and plastic wastes) with or without oxidant (H(2)O(2)). Organic acids such as acetic, formic, propionic, succinic and lactic acids were obtained in significant amounts. At 623 K (16.5 MPa), acetic acid of about 26 mg/g dry waste fish entrails was obtained. This increased to 42 mg/g dry waste fish entrails in the presence of H(2)O(2). Experiments on glucose to represent cellulosic wastes were also carried out, getting acetic acid of about 29 mg/g glucose. The study was extended to terephthalic acid and glyceraldehyde, reaction intermediates of hydrothermal treatment of polyethylene terephthalate (PET) plastic wastes and glucose, respectively. In addition, production of lactic acid, one of the interesting low-molecular-weight carboxylic acids, was discussed on the viewpoint of resources recovery. Studies on temperature dependence of formation of organic acids showed thermal stability of acetic acid, whereas, formic acid decomposed readily under hydrothermal conditions. In general, results demonstrated that the presence of oxidants favored formation of organic acids with acetic acid being the major product. PMID:12117467

  8. Hydrolysis of carboxylate ester catalyzed by a new artificial abzyme based on molecularly imprinted polymer

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    A new kind of artificial abzyme MIP-3, which contains N-phenyl benzonic amide group and “nanochannel” formed by embedded ZnO nano materials, and is imprinted by a transition-state analogue of p-nitrophenyl methyphosphonate in the hydrolysis of p-nitrophenyl acetate, was prepared by radical co-polymerization. Hydrolytic kinetics of p-nitrophenyl carboxylate catalyzed by MIP-3 was investigated. The results showed that the artificial abzyme exhibited notable substructure selectivity and strong catalytic ability in hydrolysis of p-nitrophenyl acetate

  9. The carbon isotope biogeochemistry of acetate from a methanogenic marine sediment

    Science.gov (United States)

    Blair, N. E.; Carter, W. D., Jr.

    1992-01-01

    The delta C-13 value of porewater acetate isolated from the anoxic sediments of Cape Lookout Bight (North Carolina) ranged from -17.6 percent in the sulfate reduction zone to -2.8 percent in the underlying methanogenic zone. The large C-13 enrichment in the sulfate-depleted sediments appears to be associated with the dissimilation of acetate to CH4 and CO2. Fractionation factors for that process were estimated to be 1.032 +/- 0.014 and 1.036 +/- 0.019 for the methyl and carboxyl groups. A subsurface maximum in delta C-13 of the total acetate molecule, as well as the methyl and carboxyl carbons at 10-15 cm depth within the sediment column, indicate that changes in the relative rates of acetate cycling pathways occur in the methanogenic zone. The methyl group of the acetate was depleted in C-13 by 7-14 percent relative to the carboxyl moiety. The intramolecular heterogeneity may be the result of both synthetic and catabolic isotope effects.

  10. The Microwave-assisted Preparation and X-Ray Structure of 3-Bromocarbazole-N-Acetic Acid

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The rapid synthesis of 3-bromocarbazole-N-acetic acid was performed using microwave irradiation. Under the optimal conditions the yield was 85.6 %. The crystal structure showed that the carboxylic groups form bifurcated hydrogen bonds and the hydroxyl oxygen atoms serve as proton donors and also acceptor. Each carboxylic group was involved in four hydrogen bonds. The packing of crystal was dominated by links of these hydrogen bonds.

  11. Hydrolytic activity of -alkoxide/acetato-bridged binuclear Cu(II) complexes towards carboxylic acid ester

    Indian Academy of Sciences (India)

    Weidong Jiang; Bin Xu; Zhen Xiang; Shengtian Huang; Fuan Liu; Ying Wang

    2013-09-01

    Two -alkoxide/acetate-bridged small molecule binuclear copper(II) complexes were synthesized, and used to promote the hydrolysis of a classic carboxylic acid ester, -nitrophenyl picolinate (PNPP). Both binuclear complexes exhibited good hydrolytic reactivity, giving rise to . 15547- and 17462-fold acceleration over background value for PNPP hydrolysis at neutral conditions, respectively. For comparing, activities of the other two mononuclear analogues were evaluated, revealing that binuclear complexes show approximately 150- and 171-fold kinetic advantage over their mononuclear analogues.

  12. Expressional studies of the aldehyde oxidase (AOX1) gene during myogenic differentiation in C2C12 cells

    International Nuclear Information System (INIS)

    Highlights: • AOX1 contributes to the formation of myotube. • Silencing of AOX1 reduces myotube formation. • AOX1 regulates MyoG gene expression. • AOX1 contributes to myogenesis via H2O2. - Abstract: Aldehyde oxidases (AOXs), which catalyze the hydroxylation of heterocycles and oxidation of a wide variety of aldehydic compounds, have been present throughout evolution from bacteria to humans. While humans have only a single functional aldehyde oxidase (AOX1) gene, rodents are endowed with four AOXs; AOX1 and three aldehyde oxidase homologs (AOH1, AOH2 and AOH3). In continuation of our previous study conducted to identify genes differentially expressed during myogenesis using a microarray approach, we investigated AOX1 with respect to its role in myogenesis to conceptualize how it is regulated in C2C12 cells. The results obtained were validated by silencing of the AOX1 gene. Analysis of their fusion index revealed that formation of myotubes showed a marked reduction of up to 40% in AOX1kd cells. Expression of myogenin (MYOG), one of the marker genes used to study myogenesis, was also found to be reduced in AOX1kd cells. AOX1 is an enzyme of pharmacological and toxicological importance that metabolizes numerous xenobiotics to their respective carboxylic acids. Hydrogen peroxide (H2O2) produced as a by-product in this reaction is considered to be involved as a part of the signaling mechanism during differentiation. An observed reduction in the level of H2O2 among AOX1kd cells confirmed production of H2O2 in the reaction catalyzed by AOX1. Taken together, these findings suggest that AOX1 acts as a contributor to the process of myogenesis by influencing the level of H2O2

  13. Expressional studies of the aldehyde oxidase (AOX1) gene during myogenic differentiation in C2C12 cells

    Energy Technology Data Exchange (ETDEWEB)

    Kamli, Majid Rasool; Kim, Jihoe; Pokharel, Smritee; Jan, Arif Tasleem [School of Biotechnology, Yeungnam University, Gyeongsan 712-749 (Korea, Republic of); Lee, Eun Ju [School of Biotechnology, Yeungnam University, Gyeongsan 712-749 (Korea, Republic of); Bovine Genome Resources Bank, Yeungnam University, Gyeongsan 712-749 (Korea, Republic of); Choi, Inho, E-mail: inhochoi@ynu.ac.kr [School of Biotechnology, Yeungnam University, Gyeongsan 712-749 (Korea, Republic of); Bovine Genome Resources Bank, Yeungnam University, Gyeongsan 712-749 (Korea, Republic of)

    2014-08-08

    Highlights: • AOX1 contributes to the formation of myotube. • Silencing of AOX1 reduces myotube formation. • AOX1 regulates MyoG gene expression. • AOX1 contributes to myogenesis via H{sub 2}O{sub 2}. - Abstract: Aldehyde oxidases (AOXs), which catalyze the hydroxylation of heterocycles and oxidation of a wide variety of aldehydic compounds, have been present throughout evolution from bacteria to humans. While humans have only a single functional aldehyde oxidase (AOX1) gene, rodents are endowed with four AOXs; AOX1 and three aldehyde oxidase homologs (AOH1, AOH2 and AOH3). In continuation of our previous study conducted to identify genes differentially expressed during myogenesis using a microarray approach, we investigated AOX1 with respect to its role in myogenesis to conceptualize how it is regulated in C2C12 cells. The results obtained were validated by silencing of the AOX1 gene. Analysis of their fusion index revealed that formation of myotubes showed a marked reduction of up to 40% in AOX1{sub kd} cells. Expression of myogenin (MYOG), one of the marker genes used to study myogenesis, was also found to be reduced in AOX1{sub kd} cells. AOX1 is an enzyme of pharmacological and toxicological importance that metabolizes numerous xenobiotics to their respective carboxylic acids. Hydrogen peroxide (H{sub 2}O{sub 2}) produced as a by-product in this reaction is considered to be involved as a part of the signaling mechanism during differentiation. An observed reduction in the level of H{sub 2}O{sub 2} among AOX1{sub kd} cells confirmed production of H{sub 2}O{sub 2} in the reaction catalyzed by AOX1. Taken together, these findings suggest that AOX1 acts as a contributor to the process of myogenesis by influencing the level of H{sub 2}O{sub 2}.

  14. Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry.

    Science.gov (United States)

    Bag, Soumabha; Hendricks, P I; Reynolds, J C; Cooks, R G

    2015-02-20

    Ionization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer. PMID:25682245

  15. Aldehyde concentrations in wet deposition and river waters

    International Nuclear Information System (INIS)

    The process of pollutants removal from the atmosphere can be responsible for the appearance of aldehydes in surface waters. We observed that formaldehyde, acetaldehyde, propanal, glyoxal, methylglyoxal and acetone were commonly present in precipitations as well as in surface water samples, while semi-volatile and poorly soluble aldehydes as nonanal and decanal were observed seasonally. Particularly high level of carbonyls concentration was noted after periods of drought and at the beginning of rainy periods. We estimated that ca. 40% of aldehydes from wet precipitations were delivered into river waters. The level of carbonyl concentration in river was positively correlated with specific local meteorological conditions such as solar radiation and ozone concentration, in contrast, there was negative correlation between aldehyde concentration in the river samples and the precipitation intensity. - Highlights: ► Atmosphere pollutants are responsible for the appearance of aldehydes in surface waters. ► Volatile aldehydes are commonly present in precipitations as well as in surface waters. ► Semi-volatile and poorly soluble aldehydes as nonanal and decanal were observed seasonally. ► High concentration of carbonyls were noted after periods of drought and at the beginning of rain. ► Carbonyl concentration in river is correlated to meteorological conditions

  16. Preparation and evaluation of 61Cu-thiophene-2-aldehyde thiosemicarbazone for PET studies

    International Nuclear Information System (INIS)

    Background: [61Cu]Thiophene-2-aldehyde thiosemicarbazone (61CuTATS) was prepared according to an analogy of carrier copper compound with antitumor activity, for eventual use in PET. Material and Methods: [61Cu]TATS was prepared using copper-61 acetate and in-house made ligand (TATS) in one step. 61Cu was produced via the natZn(p,x)61Cu nuclear reaction (180 eA, 22 MeV, 3.2 h) followed by a two-step chromatography method (222 GBq of 61Cu2+). 61Cu TATS preparation was optimized for reaction conditions (buffer concentration and temperature). The tracer was finally administered to normal rats for biodistribution studies. Results: Total radiolabelling of the tracer took 30 minutes with a radiochemical purity of more than 90% (using HPLC and RTLC) and specific activity of about 250-300 Ci/mmol. The complex was stable in the presence of human serum for an hour. The biodistribution of copper cation and the tracer was checked in wild-type rats for up to 2 hours with significant spleen and lung uptake of the tracer. Preparation and evaluation of 61Cu-thiophene-2-aldehyde thiosemicarbazone for PET studies. Conclusion: The production of 61Cu via the natZn(p,x)61Cu is an efficient and reproducible method with high specific activity leading to the production and preliminary evaluation of 61Cu TATS, a potential PET tracer, was reported. (authors)

  17. Preparing Process of Cerium Acetate and Rare Earth Acetate

    Institute of Scientific and Technical Information of China (English)

    Qiao Jun; Ma Ying; Xu Yanhui; Zhang Jun; Chang Shu; Hao Xianku

    2004-01-01

    Preparing process was presented and the influences of concentration of acetic acid, reaction temperature, the ratio of cerium carbonate and acetic acid, heat preservation time to the yield of cerium acetate were discussed.The crystalline cerium acetate and rare earth acetate such as ( La, Ce, Pr, Nd) (Ac) 3, ( Ce, Pr, Nd) (Ac) 3, ( Pr, Nd, Er,Y) (Ac) 3 and yttrium acetate were prepared under this condition.The shape, structure and composition of the crystals were determined by the methods of SEM, TG-DTA, X-ray diffraction and chemical analysis.The optimum prepared conditions of cerium acetate were described.This prepared process has characteristics such as simple process route, low cost, high yield, good quality, no pollution to environment, etc.

  18. Synthesis of α,β-unsaturated esters via a chemo-enzymatic chain elongation approach by combining carboxylic acid reduction and Wittig reaction

    OpenAIRE

    Yitao Duan; Peiyuan Yao; Yuncheng Du; Jinhui Feng; Qiaqing Wu; Dunming Zhu

    2015-01-01

    α,β-Unsaturated esters are versatile building blocks for organic synthesis and of significant importance for industrial applications. A great variety of synthetic methods have been developed, and quite a number of them use aldehydes as precursors. Herein we report a chemo-enzymatic chain elongation approach to access α,β-unsaturated esters by combining an enzymatic carboxylic acid reduction and Wittig reaction. Recently, we have found that Mycobacterium sp. was able to reduce phenylacetic aci...

  19. Turn on Fluorescent Probes for Selective Targeting of Aldehydes

    Directory of Open Access Journals (Sweden)

    Ozlem Dilek

    2016-03-01

    Full Text Available Two different classes of fluorescent dyes were prepared as a turn off/on sensor system for aldehydes. Amino derivatives of a boron dipyrromethene (BDP fluorophore and a xanthene-derived fluorophore (rosamine were prepared. Model compounds of their product with an aldehyde were prepared using salicylaldehyde. Both amino boron dipyrromethene and rosamine derivatives are almost non-fluorescent in polar and apolar solvent. However, imine formation with salicylaldehyde on each fluorophore increases the fluorescence quantum yield by almost a factor of 10 (from 0.05 to 0.4. These fluorophores are therefore suitable candidates for development of fluorescence-based sensors for aldehydes.

  20. Structure Property Relationships of Carboxylic Acid Isosteres.

    Science.gov (United States)

    Lassalas, Pierrik; Gay, Bryant; Lasfargeas, Caroline; James, Michael J; Tran, Van; Vijayendran, Krishna G; Brunden, Kurt R; Kozlowski, Marisa C; Thomas, Craig J; Smith, Amos B; Huryn, Donna M; Ballatore, Carlo

    2016-04-14

    The replacement of a carboxylic acid with a surrogate structure, or (bio)-isostere, is a classical strategy in medicinal chemistry. The general underlying principle is that by maintaining the features of the carboxylic acid critical for biological activity, but appropriately modifying the physicochemical properties, improved analogs may result. In this context, a systematic assessment of the physicochemical properties of carboxylic acid isosteres would be desirable to enable more informed decisions of potential replacements to be used for analog design. Herein we report the structure-property relationships (SPR) of 35 phenylpropionic acid derivatives, in which the carboxylic acid moiety is replaced with a series of known isosteres. The data set generated provides an assessment of the relative impact on the physicochemical properties that these replacements may have compared to the carboxylic acid analog. As such, this study presents a framework for how to rationally apply isosteric replacements of the carboxylic acid functional group. PMID:26967507

  1. Complicated Composting: Persistent Pyridine Carboxylic Acid Herbicides

    OpenAIRE

    Reimer, Julie

    2013-01-01

    This paper reviews pyridine carboxylic acid herbicide impacts on compost. Pyridine carboxylic acid herbicides are not completely broken down during grass growth, harvest and drying of hay, in the digestive tract of livestock, or during composting. These herbicides are a popular choice for broadleaf weed control because of this persistence: they remain effective for months or years. Pyridine carboxylic acids are also more effective than the common herbicide 2, 4-dichlorophenoxyacetic acid and ...

  2. 4-Carbamoylpiperidinium acetate monohydrate

    Directory of Open Access Journals (Sweden)

    Urs D. Wermuth

    2010-12-01

    Full Text Available In the structure of the title compound, C6H13N2O+·C2H3O2−·H2O, the amide H atoms of the cations form centrosymmetric cyclic hydrogen-bonding associations incorporating two water molecules [graph set R42(8], which are conjoint with cyclic water-bridged amide–amide associations [R44(12] and larger R44(20 associations involving the water molecule and the acetate anions, which bridge through the piperidinium H-bond donors, giving an overall three-dimensional framework structure.

  3. Palladium-Catalyzed α-Arylation of Aryl Acetic Acid Derivatives via Dienolate Intermediates with Aryl Chlorides and Bromides

    OpenAIRE

    Sha, Sheng-Chun; Zhang, Jiadi; Walsh, Patrick J.

    2015-01-01

    To date, examples of α-arylation of carboxylic acids remain scarce. Using a deprotonative cross-coupling process (DCCP), a method for palladium-catalyzed γ-arylation of aryl acetic acids with aryl halides has been developed. This protocol is applicable to a wide range of aryl bromides and chlorides. A procedure for the palladium-catalyzed α-arylation of styryl acetic acids is also described.

  4. Isobutyraldehyde production from Escherichia coli by removing aldehyde reductase activity

    Directory of Open Access Journals (Sweden)

    Rodriguez Gabriel M

    2012-06-01

    Full Text Available Abstract Background Increasing global demand and reliance on petroleum-derived chemicals will necessitate alternative sources for chemical feedstocks. Currently, 99% of chemical feedstocks are derived from petroleum and natural gas. Renewable methods for producing important chemical feedstocks largely remain unaddressed. Synthetic biology enables the renewable production of various chemicals from microorganisms by constructing unique metabolic pathways. Here, we engineer Escherichia coli for the production of isobutyraldehyde, which can be readily converted to various hydrocarbons currently derived from petroleum such as isobutyric acid, acetal, oxime and imine using existing chemical catalysis. Isobutyraldehyde can be readily stripped from cultures during production, which reduces toxic effects of isobutyraldehyde. Results We adopted the isobutanol pathway previously constructed in E. coli, neglecting the last step in the pathway where isobutyraldehyde is converted to isobutanol. However, this strain still overwhelmingly produced isobutanol (1.5 g/L/OD600 (isobutanol vs 0.14 g/L/OD600 (isobutyraldehyde. Next, we deleted yqhD which encodes a broad-substrate range aldehyde reductase known to be active toward isobutyraldehyde. This strain produced isobutanol and isobutyraldehyde at a near 1:1 ratio, indicating further native isobutyraldehyde reductase (IBR activity in E. coli. To further eliminate isobutanol formation, we set out to identify and remove the remaining IBRs from the E. coli genome. We identified 7 annotated genes coding for IBRs that could be active toward isobutyraldehyde: adhP, eutG, yiaY, yjgB, betA, fucO, eutE. Individual deletions of the genes yielded only marginal improvements. Therefore, we sequentially deleted all seven of the genes and assessed production. The combined deletions greatly increased isobutyraldehyde production (1.5 g/L/OD600 and decreased isobutanol production (0.4 g/L/OD600. By assessing production by

  5. The oxidative fermentation of ethanol in Gluconacetobacter diazotrophicus is a two-step pathway catalyzed by a single enzyme: alcohol-aldehyde Dehydrogenase (ADHa).

    Science.gov (United States)

    Gómez-Manzo, Saúl; Escamilla, José E; González-Valdez, Abigail; López-Velázquez, Gabriel; Vanoye-Carlo, América; Marcial-Quino, Jaime; de la Mora-de la Mora, Ignacio; Garcia-Torres, Itzhel; Enríquez-Flores, Sergio; Contreras-Zentella, Martha Lucinda; Arreguín-Espinosa, Roberto; Kroneck, Peter M H; Sosa-Torres, Martha Elena

    2015-01-01

    Gluconacetobacter diazotrophicus is a N2-fixing bacterium endophyte from sugar cane. The oxidation of ethanol to acetic acid of this organism takes place in the periplasmic space, and this reaction is catalyzed by two membrane-bound enzymes complexes: the alcohol dehydrogenase (ADH) and the aldehyde dehydrogenase (ALDH). We present strong evidence showing that the well-known membrane-bound Alcohol dehydrogenase (ADHa) of Ga. diazotrophicus is indeed a double function enzyme, which is able to use primary alcohols (C2-C6) and its respective aldehydes as alternate substrates. Moreover, the enzyme utilizes ethanol as a substrate in a reaction mechanism where this is subjected to a two-step oxidation process to produce acetic acid without releasing the acetaldehyde intermediary to the media. Moreover, we propose a mechanism that, under physiological conditions, might permit a massive conversion of ethanol to acetic acid, as usually occurs in the acetic acid bacteria, but without the transient accumulation of the highly toxic acetaldehyde. PMID:25574602

  6. The Oxidative Fermentation of Ethanol in Gluconacetobacter diazotrophicus Is a Two-Step Pathway Catalyzed by a Single Enzyme: Alcohol-Aldehyde Dehydrogenase (ADHa

    Directory of Open Access Journals (Sweden)

    Saúl Gómez-Manzo

    2015-01-01

    Full Text Available Gluconacetobacter diazotrophicus is a N2-fixing bacterium endophyte from sugar cane. The oxidation of ethanol to acetic acid of this organism takes place in the periplasmic space, and this reaction is catalyzed by two membrane-bound enzymes complexes: the alcohol dehydrogenase (ADH and the aldehyde dehydrogenase (ALDH. We present strong evidence showing that the well-known membrane-bound Alcohol dehydrogenase (ADHa of Ga. diazotrophicus is indeed a double function enzyme, which is able to use primary alcohols (C2–C6 and its respective aldehydes as alternate substrates. Moreover, the enzyme utilizes ethanol as a substrate in a reaction mechanism where this is subjected to a two-step oxidation process to produce acetic acid without releasing the acetaldehyde intermediary to the media. Moreover, we propose a mechanism that, under physiological conditions, might permit a massive conversion of ethanol to acetic acid, as usually occurs in the acetic acid bacteria, but without the transient accumulation of the highly toxic acetaldehyde.

  7. Synthesis of 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives

    International Nuclear Information System (INIS)

    Quinolin derivatives are a group of compounds known to possess a wide range of biological activities. The chemistry of quinolines together with their corresponding aldehydes were dealt with in chapter one of this study. Special emphasis was given to the chemistry of benzaldehyde. Twenty five 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives together with their corresponding intermediates were prepared in this work. Basically, the synthetic design of these compounds arise from the appropriate disconnections of the target 2-phenyl and 2,3-diphenyl-quinolin-4-carboxylic acids. The retro synthesis analysis of these compounds reveals pyruvic acid, aromatic amine and benzaldehyde or phenyl pyruvic acid, aromatic amine and benzaldehyde as possible logical precursors for 2-phenyl-and 2,3-diphenyl- quinoline-4-carboxylic acids respectively. The purity and identities of the synthesized compounds were elucidated through chromatographic and spectroscopic techniques. The compounds were heavily subjected to spectroscopic analysis (UV, IR, GC/MS, 1H-and 13C- NMR). The appropriate disconnections and the mechanisms of the corresponding reactions were given and discussed in chapter three. The spectral data were interpreted and correlated with the target structures. The prepared 2-phenyl- and 2,3-diphenyl-quinoline-4-carboxylic acid derivatives were screened for their antibacterial activity. The compounds were tested against the standard bacterial organisms B. subtilis, S. aureus, E. coli and P. vulgaris. Some of these compounds were devoid of antibacterial activity against S. aureus and P. vulgaris, while others showed moderate activity. All of the tested compounds showed an activity against B. subtilis and E. coli. 2,3-diphenyl -6-sulphanilamide-quinolin-4-carboxylic acid showed the highest activity against the four standard tested organisms.(Author)

  8. Threshold responses in cinnamic-aldehyde-sensitive subjects: results and methodological aspects

    DEFF Research Database (Denmark)

    Johansen, J D; Andersen, Klaus Ejner; Rastogi, S C;

    1996-01-01

    tests and 6-week graded use tests with 0.02, 0.1 and 0.8% cinnamic aldehyde in ethanol was studied in a group of cinnamic-aldehyde-sensitive eczema patients. The minimum effect level demonstrated was 0.02% cinnamic aldehyde on patch testing and 0.1% cinnamic aldehyde on use testing, which are allowed...... exposure information is needed to evaluate more fully the consequences of cinnamic aldehyde sensitivity....

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

    Science.gov (United States)

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

    2016-04-01

    Aldehydes are genotoxic and cytotoxic molecules and have received considerable attention for their associations with the pathogenesis of various human diseases. In addition, exposure to anthropogenic aldehydes increases human health risks. The general mechanism of aldehyde toxicity involves adduct formation with biomolecules such as DNA and proteins. Although the genotoxic effects of aldehydes such as mutations and chromosomal aberrations are directly related to DNA damage, the role of DNA damage in the cytotoxic effects of aldehydes is poorly understood because concurrent protein damage by aldehydes has similar effects. In this study, we have analysed how saturated and α,β-unsaturated aldehydes exert cytotoxic effects through DNA and protein damage. Interestingly, DNA repair is essential for alleviating the cytotoxic effect of weakly toxic aldehydes such as saturated aldehydes but not highly toxic aldehydes such as long α,β-unsaturated aldehydes. Thus, highly toxic aldehydes inactivate cells exclusively by protein damage. Our data suggest that DNA interstrand crosslinks, but not DNA-protein crosslinks and DNA double-strand breaks, are the critical cytotoxic DNA damage induced by aldehydes. Further, we show that the depletion of intracellular glutathione and the oxidation of thioredoxin 1 partially account for the DNA damage-independent cytotoxicity of aldehydes. On the basis of these findings, we have proposed a mechanistic model of aldehyde cytotoxicity mediated by DNA and protein damage. PMID:26917342

  10. Aldehyde Dehydrogenase Gene Superfamily in Populus: Organization and Expression Divergence between Paralogous Gene Pairs.

    Directory of Open Access Journals (Sweden)

    Feng-Xia Tian

    Full Text Available Aldehyde dehydrogenases (ALDHs constitute a superfamily of NAD(P+-dependent enzymes that catalyze the irreversible oxidation of a wide range of reactive aldehydes to their corresponding nontoxic carboxylic acids. ALDHs have been studied in many organisms from bacteria to mammals; however, no systematic analyses incorporating genome organization, gene structure, expression profiles, and cis-acting elements have been conducted in the model tree species Populus trichocarpa thus far. In this study, a comprehensive analysis of the Populus ALDH gene superfamily was performed. A total of 26 Populus ALDH genes were found to be distributed across 12 chromosomes. Genomic organization analysis indicated that purifying selection may have played a pivotal role in the retention and maintenance of PtALDH gene families. The exon-intron organizations of PtALDHs were highly conserved within the same family, suggesting that the members of the same family also may have conserved functionalities. Microarray data and qRT-PCR analysis indicated that most PtALDHs had distinct tissue-specific expression patterns. The specificity of cis-acting elements in the promoter regions of the PtALDHs and the divergence of expression patterns between nine paralogous PtALDH gene pairs suggested that gene duplications may have freed the duplicate genes from the functional constraints. The expression levels of some ALDHs were up- or down-regulated by various abiotic stresses, implying that the products of these genes may be involved in the adaptation of Populus to abiotic stresses. Overall, the data obtained from our investigation contribute to a better understanding of the complexity of the Populus ALDH gene superfamily and provide insights into the function and evolution of ALDH gene families in vascular plants.

  11. Aldehyde oxidase activity in fresh human skin.

    Science.gov (United States)

    Manevski, Nenad; Balavenkatraman, Kamal Kumar; Bertschi, Barbara; Swart, Piet; Walles, Markus; Camenisch, Gian; Schiller, Hilmar; Kretz, Olivier; Ling, Barbara; Wettstein, Reto; Schaefer, Dirk J; Pognan, Francois; Wolf, Armin; Litherland, Karine

    2014-12-01

    Human aldehyde oxidase (AO) is a molybdoflavoenzyme that commonly oxidizes azaheterocycles in therapeutic drugs. Although high metabolic clearance by AO resulted in several drug failures, existing in vitro-in vivo correlations are often poor and the extrahepatic role of AO practically unknown. This study investigated enzymatic activity of AO in fresh human skin, the largest organ of the body, frequently exposed to therapeutic drugs and xenobiotics. Fresh, full-thickness human skin was obtained from 13 individual donors and assayed with two specific AO substrates: carbazeran and zoniporide. Human skin explants from all donors metabolized carbazeran to 4-hydroxycarbazeran and zoniporide to 2-oxo-zoniporide. Average rates of carbazeran and zoniporide hydroxylations were 1.301 and 0.164 pmol⋅mg skin(-1)⋅h(-1), resulting in 13 and 2% substrate turnover, respectively, after 24 hours of incubation with 10 μM substrate. Hydroxylation activities for the two substrates were significantly correlated (r(2) = 0.769), with interindividual variability ranging from 3-fold (zoniporide) to 6-fold (carbazeran). Inclusion of hydralazine, an irreversible inhibitor of AO, resulted in concentration-dependent decrease of hydroxylation activities, exceeding 90% inhibition of carbazeran 4-hydroxylation at 100 μM inhibitor. Reaction rates were linear up to 4 hours and well described by Michaelis-Menten enzyme kinetics. Comparison of carbazeran and zoniporide hydroxylation with rates of triclosan glucuronidation and sulfation and p-toluidine N-acetylation showed that cutaneous AO activity is comparable to tested phase II metabolic reactions, indicating a significant role of AO in cutaneous drug metabolism. To our best knowledge, this is the first report of AO enzymatic activity in human skin. PMID:25249692

  12. Sorption Behavior of an Aliphatic Series of Aldehydes in the Presence of Poly(ethylene terephthalate) Blends Containing Aldehyde Scavenging Agents

    OpenAIRE

    Suloff, Eric Charles

    2002-01-01

    The quality of many beverages and food products is compromised by the presence of low molecular weight aldehydes. Aldehydes are commonly formed during storage by the oxidation of lipids or are introduced as migrants from polymeric packaging material. The objective of this project was to evaluate the effectiveness of three aldehyde scavenging agents, blended into poly(ethylene terephthalate) (PET) films, in removing an aliphatic series of aldehydes from an acidified aqueous model solution (p...

  13. ACETIC ACID AND A BUFFER

    DEFF Research Database (Denmark)

    2009-01-01

    The present invention relates to a composition comprising : a) 0.01-20% wt/wt acetic acid and b) a physiologically tolerable buffer capable of maintaining acetic acid at a pH in the range of 2-7; and use of such a composition as an antimicrobial agent.......The present invention relates to a composition comprising : a) 0.01-20% wt/wt acetic acid and b) a physiologically tolerable buffer capable of maintaining acetic acid at a pH in the range of 2-7; and use of such a composition as an antimicrobial agent....

  14. Sm(II)-Mediated Electron Transfer to Carboxylic Acid Derivatives: Development of Complexity-Generating Cascades.

    Science.gov (United States)

    Just-Baringo, Xavier; Procter, David J

    2015-05-19

    Reductive electron transfer (ET) to organic compounds is a powerful method for the activation of substrates via the formation of radicals, radical anions, anions, and dianions that can be exploited in bond-cleaving and bond-forming processes. Since its introduction to the synthetic community in 1977 by Kagan, SmI2 has become one of the most important reducing agents available in the laboratory. Despite its widespread application in aldehyde and ketone reduction, it was widely accepted that carboxylic acid derivatives could not be reduced by SmI2; only recently has our work led to this dogma being overturned, and the reduction of carboxylic acid derivatives using SmI2 can now take its place alongside aldehyde/ketone reduction as a powerful activation mode for synthesis. In this Account, we set out our studies of the reduction of carboxylic acid derivatives using SmI2, SmI2-H2O, and SmI2-H2O-NR3 and the exploitation of the unusual radical anions that are now accessible in unprecedented carbon-carbon bond-forming processes. The Account begins with our serendipitous discovery that SmI2 mixed with H2O is able to reduce six-membered lactones to diols, a transformation previously thought to be impossible. After the successful development of selective monoreductions of Meldrum's acid and barbituric acid heterocyclic feedstocks, we then identified the SmI2-H2O-NR3 reagent system for the efficient reduction of a range of acyclic carboxylic acid derivatives that typically present a significant challenge for ET reductants. Mechanistic studies have led us to propose a common mechanism for the reduction of carboxylic acid derivatives using Sm(II), with only subtle changes observed as the carboxylic acid derivative and Sm(II) reagent system are varied. At the center of our postulated mechanism is the proposed reversibility of the first ET to the carbonyl of carboxylic acid derivatives, and this led us to devise several strategies that allow the radical anion intermediates to be

  15. Synthesis of α,β-unsaturated esters via a chemo-enzymatic chain elongation approach by combining carboxylic acid reduction and Wittig reaction

    Directory of Open Access Journals (Sweden)

    Yitao Duan

    2015-11-01

    Full Text Available α,β-Unsaturated esters are versatile building blocks for organic synthesis and of significant importance for industrial applications. A great variety of synthetic methods have been developed, and quite a number of them use aldehydes as precursors. Herein we report a chemo-enzymatic chain elongation approach to access α,β-unsaturated esters by combining an enzymatic carboxylic acid reduction and Wittig reaction. Recently, we have found that Mycobacterium sp. was able to reduce phenylacetic acid (1a to 2-phenyl-1-ethanol (1c and two sequences in the Mycobacterium sp. genome had high identity with the carboxylic acid reductase (CAR gene from Nocardia iowensis. These two putative CAR genes were cloned, overexpressed in E. coli and one of two proteins could reduce 1a. The recombinant CAR was purified and characterized. The enzyme exhibited high activity toward a variety of aromatic and aliphatic carboxylic acids, including ibuprofen. The Mycobacterium CAR catalyzed carboxylic acid reduction to give aldehydes, followed by a Wittig reaction to afford the products α,β-unsaturated esters with extension of two carbon atoms, demonstrating a new chemo-enzymatic method for the synthesis of these important compounds.

  16. Synthesis of α,β-unsaturated esters via a chemo-enzymatic chain elongation approach by combining carboxylic acid reduction and Wittig reaction.

    Science.gov (United States)

    Duan, Yitao; Yao, Peiyuan; Du, Yuncheng; Feng, Jinhui; Wu, Qiaqing; Zhu, Dunming

    2015-01-01

    α,β-Unsaturated esters are versatile building blocks for organic synthesis and of significant importance for industrial applications. A great variety of synthetic methods have been developed, and quite a number of them use aldehydes as precursors. Herein we report a chemo-enzymatic chain elongation approach to access α,β-unsaturated esters by combining an enzymatic carboxylic acid reduction and Wittig reaction. Recently, we have found that Mycobacterium sp. was able to reduce phenylacetic acid (1a) to 2-phenyl-1-ethanol (1c) and two sequences in the Mycobacterium sp. genome had high identity with the carboxylic acid reductase (CAR) gene from Nocardia iowensis. These two putative CAR genes were cloned, overexpressed in E. coli and one of two proteins could reduce 1a. The recombinant CAR was purified and characterized. The enzyme exhibited high activity toward a variety of aromatic and aliphatic carboxylic acids, including ibuprofen. The Mycobacterium CAR catalyzed carboxylic acid reduction to give aldehydes, followed by a Wittig reaction to afford the products α,β-unsaturated esters with extension of two carbon atoms, demonstrating a new chemo-enzymatic method for the synthesis of these important compounds. PMID:26664647

  17. Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

    Directory of Open Access Journals (Sweden)

    M. Vaïtilingom

    2011-08-01

    Full Text Available The objective of this work was to compare experimentally the contribution of photochemistry vs. microbial activity to the degradation of carboxylic acids present in cloud water. For this, we selected 17 strains representative of the microflora existing in real clouds and worked on two distinct artificial cloud media that reproduce marine and continental cloud chemical composition. Photodegradation experiments with hydrogen peroxide (H2O2 as a source of hydroxyl radicals were performed under the same microcosm conditions using two irradiation systems. Biodegradation and photodegradation rates of acetate, formate, oxalate and succinate were measured on both media at 5 °C and 17 °C and were shown to be on the same order of magnitude (around 10−10–10−11 M s−1. The chemical composition (marine or continental origin had little influence on photodegradation and biodegradation rates while the temperature shift from 17 °C to 5 °C decreased biodegradation rates of a factor 2 to 5.

    In order to test other photochemical scenarios, theoretical photodegradation rates were calculated considering hydroxyl (OH radical concentration values in cloud water estimated by cloud chemistry modelling studies and available reaction rate constants of carboxylic compounds with both hydroxyl and nitrate radicals. Considering high OH concentration ([OH] = 1 × 10−12 M led to no significant contribution of microbial activity in the destruction of carboxylic acids. On the contrary, for lower OH concentration (at noon, [OH] = 1 × 10−14 M, microorganisms could efficiently compete with photochemistry and in similar contributions than the ones estimated by our experimental approach.

    Combining these two approaches (experimental and theoretical, our results led to the following conclusions: oxalate was only photodegraded; the photodegradation of formate was usually more

  18. Protection of historical lead against acetic acid vapour

    Directory of Open Access Journals (Sweden)

    Pecenová Z.

    2016-03-01

    Full Text Available Historical lead artefacts (small figurines, appliques, bull (metal seal can be stored in depository and archives in inconvenient storage conditions. The wooden show-case or paper packagings release volatile organic compound to the air during their degradation. These acids, mainly acetic acid are very corrosive for lead. The thin layer of corrosion products which slows atmospheric corrosion is formed on lead surface in atmospheric condition. In presence of acetic acid vapour the voluminous corrosion products are formed and fall off the surface. These corrosion products do not have any protection ability. The lead could be protected against acid environment by layer of “metal soup” which is formed on surface after immersion in solution of salt of carboxylic acid for 24 hours. The solutions of acids (with vary long of carbon chain and their salts are examined. Longer carbon chain provides better efficiency convers layer. The disadvantages are low solubility of carboxylic acids in water and bad abrasion resistance of formed layer.

  19. Reaction of tobacco smoke aldehydes with human hemoglobin.

    Science.gov (United States)

    Hoberman, H D; San George, R C

    1988-01-01

    Formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, and acrolein, all of which are constituents of tobacco smoke, were reacted in 5 mM concentration with the purified major fraction of normal adult human hemoglobin (hemoglobin Ao) in 1 mM concentration. A cigarette smoke condensate, diluted to contain 5 mM total aldehydes, was also reacted with 1 mM hemoglobin Ao. Cationic exchange high-performance liquid chromatography (HPLC) showed that the products formed from simple aliphatic aldehydes, with the exception of formaldehyde, were analogues of those formed from acetaldehyde, earlier shown by us to be imidazolidinone derivatives, that is, cyclic addition products of the N-terminal aminoamide function of alpha and beta chains. Formaldehyde and acrolein produced a heterogeneous mixture of derivatives including cross-linked hemoglobin dimers. The greater proportion of modified hemoglobins produced by condensate aldehydes resembled those formed from acetaldehyde, the most abundant aldehyde in the condensate. A smaller fraction consisted of cross-linked hemoglobin dimers, presumably due to the action of formaldehyde. Mass spectrometric and HPLC analyses of the 2,4-dinitrophenylhydrazones precipitated from the condensate documented the presence of formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, furfural, and methylfurfural. The toxicity of aldehydes is briefly discussed in the context of the findings of this study. PMID:3236330

  20. Carboxylation and anaplerosis in neurons and glia.

    Science.gov (United States)

    Hassel, B

    2000-01-01

    Anaplerosis, or de novo formation of intermediates of the tricarboxylic acid (TCA) cycle, compensates for losses of TCA cycle intermediates, especially alpha-ketoglutarate, from brain cells. Loss of alpha-ketoglutarate occurs through release of glutamate and GABA from neurons and through export of glutamine from glia, because these amino acids are alpha-ketoglutarate derivatives. Anaplerosis in the brain may involve four different carboxylating enzymes: malic enzyme, phosphoenopyruvate carboxykinase (PEPCK), propionyl-CoA carboxylase, and pyruvate carboxylase. Anaplerotic carboxylation was for many years thought to occur only in glia through pyruvate carboxylase; therefore, loss of transmitter glutamate and GABA from neurons was thought to be compensated by uptake of glutamine from glia. Recently, however, anaplerotic pyruvate carboxylation was demonstrated in glutamatergic neurons, meaning that these neurons to some extent can maintain transmitter synthesis independently of glutamine. Malic enzyme, which may carboxylate pyruvate, was recently detected in neurons. The available data suggest that neuronal and glial pyruvate carboxylation could operate at as much as 30% and 40-60% of the TCA cycle rate, respectively. Cerebral carboxylation reactions are probably balanced by decarboxylation reactions,, because cerebral CO2 formation equals O2 consumption. The finding of pyruvate carboxylation in neurons entails a major revision of the concept of the glutamine cycle. PMID:11414279

  1. INVESTIGATION OF THE CHEMICAL STRUCTURE OF CARBOXYLATED AND CARBOXYMETHYLATED FIBERS FROM WASTE PAPER VIA XRD AND FTIR ANALYSIS

    Directory of Open Access Journals (Sweden)

    Mohammad Mohkami Mail

    2011-04-01

    Full Text Available This paper describes preparation of carboxymethylated and carboxylated cellulosic fibers from waste paper. Chemical properties of the product were distinguished by Fourier-transform infrared (FTIR spectroscopy and X-ray diffraction (XRD spectral analysis. To produce carboxylated and crosslinked fibers and also to increase the anionic surface charge of the fibers, maleic anhydride was used in three different batches; 0, 1%, and 5%. The treatment condition for producing carboxymethylated fibers also involved the use of isopropanol, sodium hydroxide solution, and monochloroacetic acid. The product was purified with 70/30 methanol/ water. Then one sample was neutralized with acetic acid and the other was considered as a sample without having been neutralized. Effects of these treatments were evaluated by FTIR and XRD analysis. The results of FTIR analysis indicated that the carboxyl and methyl functional groups had increased in the carboxymethylated fibers and that just carboxyl groups had increased in carboxylated fibers. The results of XRD analysis showed that the crystallinity of cellulose had decreased in both the carboxymethylated and carboxylated fibers.

  2. Maternal aldehyde elimination during pregnancy preserves the fetal genome.

    Science.gov (United States)

    Oberbeck, Nina; Langevin, Frédéric; King, Gareth; de Wind, Niels; Crossan, Gerry P; Patel, Ketan J

    2014-09-18

    Maternal metabolism provides essential nutrients to enable embryonic development. However, both mother and embryo produce reactive metabolites that can damage DNA. Here we discover how the embryo is protected from these genotoxins. Pregnant mice lacking Aldh2, a key enzyme that detoxifies reactive aldehydes, cannot support the development of embryos lacking the Fanconi anemia DNA repair pathway gene Fanca. Remarkably, transferring Aldh2(-/-)Fanca(-/-) embryos into wild-type mothers suppresses developmental defects and rescues embryonic lethality. These rescued neonates have severely depleted hematopoietic stem and progenitor cells, indicating that despite intact maternal aldehyde catabolism, fetal Aldh2 is essential for hematopoiesis. Hence, maternal and fetal aldehyde detoxification protects the developing embryo from DNA damage. Failure of this genome preservation mechanism might explain why birth defects and bone marrow failure occur in Fanconi anemia, and may have implications for fetal well-being in the many women in Southeast Asia that are genetically deficient in ALDH2. PMID:25155611

  3. Highly active catalyst for vinyl acetate synthesis by modified activated carbon

    Institute of Scientific and Technical Information of China (English)

    Chun Yan Hou; Liang Rong Feng; Fa Li Qiu

    2009-01-01

    A new zinc acetate catalyst which was prepared from modified activated carbon exhibited extreme activity towards the synthesis of vinyl acetate. The activated carbon was modified by nitric acid, vitriol and peroxyacetic acid (PAA). The effect on specific area, structure, pH and surface acidity groups of carriers by modification was discussed. Amount of carbonyl and carboxyl groups in activated carbon was increased by peroxyacetic acid treatment. The productivity of the new catalyst was 14.58% higher than that of catalyst prepared using untreated activated carbon. The relationship between amount of carbonyl and carboxyl groups (m) and catalyst productivity (P) was P = 1.83 + 2.26 x 10-3e3.17m. Reaction mechanism was proposed.

  4. Enzymes involved in vinyl acetate decomposition by Pseudomonas fluorescens PCM 2123 strain.

    Science.gov (United States)

    Szczyrba, Elżbieta; Greń, Izabela; Bartelmus, Grażyna

    2014-03-01

    Esterases are widely used in food processing industry, but there is little information concerning enzymes involved in decompositions of esters contributing to pollution of environment. Vinyl acetate (an ester of vinyl alcohol and acetic acid) is a representative of volatile organic compounds (VOCs) in decomposition, of which hydrolyses and oxidoreductases are mainly involved. Their activities under periodically changing conditions of environment are essential for the removal of dangerous VOCs. Esterase and alcohol/aldehyde dehydrogenase activities were determined in crude cell extract from Pseudomonas fluorescens PMC 2123 after vinyl acetate induction. All examined enzymes exhibit their highest activity at 30-35 °C and pH 7.0-7.5. Esterase preferably hydrolyzed ester bonds with short fatty chains without plain differences for C2 or C4. Comparison of Km values for alcohol and aldehyde dehydrogenases for acetaldehyde suggested that this metabolite was preferentially oxidized than reduced. Activity of alcohol dehydrogenase reducing acetaldehyde to ethanol suggested that one mechanism of defense against the elevated concentration of toxic acetaldehyde could be its temporary reduction to ethanol. Esterase activity was inhibited by phenylmethanesulfonyl fluoride, while β-mercaptoethanol, dithiothreitol, and ethylenediaminetetraacetic acid had no inhibitor effect. From among metal ions, only Mg(2+) and Fe(2+) stimulated the cleavage of ester bond. PMID:23913099

  5. Catalytic Combustion of Ethyl Acetate

    OpenAIRE

    ÖZÇELİK, Tuğba GÜRMEN; ATALAY, Süheyda; ALPAY, Erden

    2007-01-01

    The catalytic combustion of ethyl acetate over prepared metal oxide catalysts was investigated. CeO, Co2O3, Mn2O3, Cr2O3, and CeO-Co2O3 catalysts were prepared on monolith supports and they were tested. Before conducting the catalyst experiments, we searched for the homogeneous gas phase combustion reaction of ethyl acetate. According to the homogeneous phase experimental results, 45% of ethyl acetate was converted at the maximum reactor temperature tested (350 °C). All the prepare...

  6. Development of a microfluidic paper-based analytical device for the determination of salivary aldehydes.

    Science.gov (United States)

    Ramdzan, Adlin N; Almeida, M Inês G S; McCullough, Michael J; Kolev, Spas D

    2016-05-01

    A low cost, disposable and easy to use microfluidic paper-based analytical device (μPAD) was developed for simple and non-invasive determination of total aldehydes in saliva with a potential to be used in epidemiological studies to assess oral cancer risk. The μPAD is based on the colour reaction between aldehydes (e.g. acetaldehyde, formaldehyde), 3-methyl-2-benzothiazolinone hydrazone (MBTH) and iron(III) to form an intense blue coloured formazan dye. The newly developed μPAD has a 3D design with two overlapping paper layers. The first layer comprises 15 circular detection zones (8 mm in diameter), each impregnated with 8 μL of MBTH, while the second layer contains 15 reagent zones (4 mm in diameter). Two μL of iron(III) chloride are added to each one of the second layer zones after the addition of sample to the detection zones in the first layer. All hydrophilic zones of the μPAD are defined by wax printing using a commercial wax printer. Due to the 2-step nature of the analytical reaction, the two paper layers are separated by a cellulose acetate interleaving sheet to allow for the reaction between the aldehydes in the saliva sample with MBTH to proceed first with the formation of an azine, followed by a blue coloured reaction between the azine and the oxidized by iron(III) form of MBTH, produced after the removal of the interleaving sheet. After obtaining a high resolution image of the detection side zone of the device using a flatbed scanner, the intensity of the blue colour within each detection zone is measured with Image J software. Under optimal conditions, the μPAD is characterised by a working range of 20.4-114.0 μM, limit of detection of 6.1 μM, and repeatability, expressed as RSD, of less than 12.7% (n = 5). There is no statistically significant difference at the 95% confidence level between the results obtained by the μPAD and the reference method (Student's t-test: 0.090 < 0.38). The optimized μPAD is stable for more than 41 days

  7. Catalytic conversion of carboxylic acids in bio-oil for liquid hydrocarbons production

    International Nuclear Information System (INIS)

    Bio-oil must be upgraded to be suitable for use as a high-grade transport fuel. Crude bio-oil has a high content of carboxylic acids which can cause corrosion, and the high oxygen content of these acids also reduces the oil’s heating value. In this paper, acetic acid and propanoic acid were chosen as the model carboxylic acids in bio-oil. Their behavior in the production of liquid hydrocarbons during a catalytic conversion process was investigated in a micro-fixed bed reactor. The liquid organic phase from this catalytic conversion process mainly consisted of liquid hydrocarbons and phenol derivatives. Under the condition of low Liquid Hourly Space Velocity (LHSV), the liquid organic phase from acetic acid cracking had a selectivity of 22% for liquid hydrocarbons and a selectivity of 65% for phenol derivatives. The composition of the organic products changed considerably with the LHSV increasing to 3 h−1. The selectivity for liquid hydrocarbons increased up to 52% while that for phenol derivatives decreased to 32%. Propanoic acid performed much better in producing liquid hydrocarbons than acetic acid. Its selectivity for liquid hydrocarbons was as high as 80% at LHSV = 3 h−1. A mechanism for this catalytic conversion process was proposed according to the analysis of the components in the liquid organic phases. The pathways of the main compounds formation in the liquid organic phases were proposed, and the reason why liquid hydrocarbons were more effectively produced when using propanoic acid rather than acetic acid was also successfully explained. In addition, BET and SEM characterization were used to analyze the catalyst coke deposition. -- Graphical abstract: Display Omitted Highlights: ► High content of carboxylic acids in bio-oil causes its corrosiveness. ► Acetic acid and propanoic acid are two dominant acids in bio-oil. ► Liquid hydrocarbons were produced by cracking of these two dominant acids. ► A mechanism model was proposed to explain the

  8. Intermolecular cycloaddition of nonstabilized azomethine ylides generated from 1,3-thiazolidine-4-carboxylic acids: synthesis of 5,7a-dihydro-1H,3H-pyrrolo[1,2-c]thiazoles

    OpenAIRE

    Cardoso, Ana L.; Kaczor, Agnieszka; Silva, Artur M. S.; Fausto, Rui; Melo, Teresa M.V.D. Pinho e; Gonsalves, António M. D'A Rocha

    2006-01-01

    The 1,3-dipolar cycloaddition of dimethyl acetylenedicarboxylate with nonstabilized azomethine ylides, generated via the decarboxylative condensation of 1,3-thiazolidine-4-carboxylic acids with aldehydes, afforded 5,7a-dihydro-1H,3H-pyrrolo[1,2-c]thiazole derivatives. 2-Substituted-1,3-thiazolidine-4-carboxylic acids led to the stereoselective formation of 5,7a-dihydro-1H,3H-pyrrolo[1,2-c]thiazoles. Quantum-chemistry calculations were carried out allowing the rationalization of the observed s...

  9. Combining a flow reactor with spray dryer to allow the preparation of food-grade quality sodium 2-polyhydroxyalkyl-1,3-thiazolidine-4-carboxylates with a low environmental impact

    OpenAIRE

    Novo, Olalla; Balcells Fluvià, Mercè; Canela i Garayoa, Ramon; Eras i Joli, Jordi

    2016-01-01

    The 1,3-thiazolidine-4-carboxylic acid (TCA) and 2-substituted 1,3-thiazolidine-4-carboxylic acids (2S-TCAs) are used as additive prodrugs of cysteine and glutathione in agronomy and in the food and pharmaceutical industries. Using a flow system coupled to a spray dryer, here we prepared the sodium salts of these compounds in powder form. The reaction was carried out using equimolar ratios of L-cysteine, aldehyde, and sodium hydroxide in water as solvent. Formaldehyde, three aldohexoses (D-gl...

  10. Effects of aldehydes on the growth and lipid accumulation of oleaginous yeast Trichosporon fermentans.

    Science.gov (United States)

    Huang, Chao; Wu, Hong; Liu, Qiu-ping; Li, Yuan-yuan; Zong, Min-hua

    2011-05-11

    The effects of five representative aldehydes in lignocellulosic hydrolysates on the growth and the lipid accumulation of oleaginous yeast Trichosporon fermentans were investigated for the first time. There was no relationship between the hydrophobicity and the toxicity of aldehyde, and 5-hydroxymethylfurfural was less toxic than aromatic aldehydes and furfural. Binary combination of aromatic aldehydes caused a synergistic inhibitory effect, but combination of furan and aromatic aldehydes reduced the inhibition instead. A longer lag phase was found due to the presence of aldehydes and the decrease of sugar consumption rate, but more xylose was utilized by T. fermentans in the presence of aldehydes, especially at their low concentrations. The variation of malic enzyme activity was not related to the delay of lipid accumulation. Furthermore, the inhibition of aldehydes on cell growth was more dependent on inoculum size, temperature, and initial pH than that on lipid content. PMID:21443267

  11. Acetate metabolism in Methanothrix soehngenii.

    OpenAIRE

    Jetten, M. S. M.

    1991-01-01

    Acetate is quantitatively the most important intermediate in the anaerobic degradation of soluble organic matter. The conversion rate of acetate by methanogenic bacteria is proposed to be the rate limiting step in this degradation The study of acetoclastic methanogens, therefore is of relevance to our understanding of anaerobic processes and their optimal application in treatment of waste water from various sources.Until now only two genera of methane bacteria have been described which are ab...

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

    OpenAIRE

    Rizzo, William B.

    2013-01-01

    Normal fatty aldehyde and alcohol metabolism is essential for epidermal differentiation and function. Long-chain aldehydes are produced by catabolism of several lipids including fatty alcohols, sphingolipids, ether glycerolipids, isoprenoid alcohols and certain aliphatic lipids that undergo α- or ω-oxidation. The fatty aldehyde generated by these pathways is chiefly metabolized to fatty acid by fatty aldehyde dehydrogenase (FALDH, alternately known as ALDH3A2), which also functions to oxidize...

  13. Tandem Aldol Condensation – Platinacycle-Catalyzed Addition Reactions of Aldehydes, Methyl Ketones and Arylboronic Acids

    OpenAIRE

    Liao, Yuan-Xi; Hu, Qiao-Sheng

    2012-01-01

    Tandem aldol condensation of aldehydes with methyl ketones followed by anionic four-electron donor-based (Type I) platinacycle-catalyzed addition reactions of arylboronic acids to form β-arylated ketones is described. Good to excellent yields of β-arylated ketones were obtained for the tandem reactions of aromatic/aliphatic aldehydes, methyl ketones and arylboronic acids, and moderate yields were observed for the tandem reaction with α, β-unsaturated aldehydes as the aldehyde source.

  14. Changes in nonpolar aldehydes in bean cotyledons during ageing

    Czech Academy of Sciences Publication Activity Database

    Wilhelmová, Naděžda; Domingues, P.; Srbová, M.; Fuksová, H.; Wilhelm, J.

    2006-01-01

    Roč. 50, č. 4 (2006), s. 559-564. ISSN 0006-3134 R&D Projects: GA ČR GA522/03/0312 Institutional research plan: CEZ:AV0Z50380511 Keywords : Ageing * aldehydes * lipid peroxidation * lipofuscin-like pigments (LFP) Subject RIV: CE - Biochemistry Impact factor: 1.198, year: 2006

  15. A thermostable transketolase evolved for aliphatic aldehyde acceptors.

    Science.gov (United States)

    Yi, Dong; Saravanan, Thangavelu; Devamani, Titu; Charmantray, Franck; Hecquet, Laurence; Fessner, Wolf-Dieter

    2015-01-11

    Directed evolution of the thermostable transketolase from Geobacillus stearothermophilus based on a pH-based colorimetric screening of smart libraries yielded several mutants with up to 16-fold higher activity for aliphatic aldehydes and high enantioselectivity (>95% ee) in the asymmetric carboligation step. PMID:25415647

  16. Copepod reproduction is unaffected by diatom aldehydes or lipid composition

    DEFF Research Database (Denmark)

    Dutz, Jörg; Koski, Marja; Jonasdottir, Sigrun

    2008-01-01

    production of Temora longicornis were measured for six different diatom species as well as for a nondiatom control diet (Rhodomonas sp.). The experiments were accompanied by determinations of fatty acids, sterols, and polyunsaturated aldehydes (PUA) in the food. Although diatoms were generally ingested at...

  17. Reaction of benzoxasilocines with aromatic aldehydes: Synthesis of homopterocarpans

    Directory of Open Access Journals (Sweden)

    Rodríguez-García Ignacio

    2007-02-01

    Full Text Available Abstract Condensation of 2H-benzo[g][1,2]oxasilocines with aromatic aldehydes in the presence of boron trifluoride affords mixtures of cis/trans 2-phenyl-3-vinylchromans with moderate yields. These can be transformed into homopterocarpans, a synthetic group of substances homologous to the natural isoflavonoid pterocarpans.

  18. Unsaturated aldehydes as alkene equivalents in the Diels-Alder reaction

    DEFF Research Database (Denmark)

    Taarning, Esben; Madsen, Robert

    2008-01-01

    A one-pot procedure is described for using alpha,beta-unsaturated aldehydes as olefin equivalents in the Diels-Alder reaction. The method combines the normal electron demand cycloaddition with aldehyde dienophiles and the rhodium-catalyzed decarbonylation of aldehydes to afford cyclohexenes with no...

  19. CATALYTIC ESTERIFICATION OF CARBOXYLIC ACIDS WITH ALCOHOLS BY SULFO—POLYVINYL CHLORIDE

    Institute of Scientific and Technical Information of China (English)

    YuShanxin; ZHAOZongbao; 等

    1993-01-01

    Polyvinyl Chloride reacted with chlorosulfonic acid to from a polymer catalyst PVC-SO3H.This polymer catalyst was found to have high activity for resterification reaction between carboxylic acids and alcohols.This paper deals with the conditions in synthesis of n-butlyacetate catalyzed with PVC-SO3H.The PVC-SO3H was used as a catalyst for preparing 11 esters of acetic acid,propionic acid and butyric acid with the yields of 82-92%.

  20. Crystallization and preliminary X-ray analysis of l-azetidine-2-carboxylate hydrolase from Pseudomonas sp. strain A2C

    International Nuclear Information System (INIS)

    l-Azetidine-2-carboxylate hydrolase from Pseudomonas sp. strain A2C was crystallized and diffraction data were collected to a resolution of 1.38 Å. l-Azetidine-2-carboxylate hydrolase from Pseudomonas sp. strain A2C catalyzes a ring-opening reaction that detoxifies l-azetidine-2-carboxylate, an analogue of l-proline. Recombinant l-azetidine-2-carboxylate hydrolase was overexpressed, purified and crystallized using polyethylene glycol and magnesium acetate as precipitants. The needle-shaped crystal belonged to space group P21, with unit-cell parameters a = 35.6, b = 63.6, c = 54.7 Å, β = 105.5°. The crystal diffracted to a resolution of 1.38 Å. The calculated VM value was 2.2 Å3 Da−1, suggesting that the crystal contains one enzyme subunit in the asymmetric unit

  1. Recovery of propylene glycol from dilute aqueous solutions via reversible reaction with aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Broekhuis, R.R.; Lynn, S.; King, C.J. [Univ. of California, Berkeley, CA (United States). Dept. of Chemical Engineering]|[Lawrence Berkeley Lab., CA (United States)

    1993-12-01

    A means is proposed for separating propylene glycol and other compounds bearing multiple hydroxyl groups by reversible chemical reaction. Glycols react with aldehydes in cyclic acetalization reactions to form substituted dioxolanes. Propylene glycol reacts with formaldehyde and acetaldehyde to form 4-methyl-1,3-dioxolane and 2,4-dimethyl-1,3-dioxolane. The reaction is catalyzed homogeneously by strong mineral acids or heterogeneously by cation exchange resins in the acid form. Separation processes utilizing this reaction would include an acetalization step, several distillative separation steps and finally a hydrolysis step in which the reaction is reversed. Both reaction steps must be forced to completion by removing the reaction product simultaneously. The equilibrium and kinetics of the reaction with formaldehyde were studied experimentally in systems catalyzed by Amberlite IR-120 ion exchange resin. A number of solvents were screened for their ability to extract 2,4-dimethyl-1,3-dioxolane from aqueous solution. Aromatic hydrocarbons exhibited the highest distribution into the organic phase. To achieve an effective separation of propylene glycol from aqueous solution by combined reaction with formaldehyde and distillation, formaldehyde would have to be present in excess and would be difficult and costly to separate from the aqueous solution. In reactive distillation using acetaldehyde as a reactant this is not a problem. A large flow of acetaldehyde would be necessary to recover the propylene glycol sufficiently in a distillative process. In a process combining reaction and extraction into an organic solvent this problem is avoided. Process simulation indicates the energy input of such a process is less than half of the energy required in a triple-effect evaporation process. This benefit is offset by higher capital costs and increased complexity in the reaction/extraction process.

  2. EPOXY RESINS TOUGHENED WITH CARBOXYL TERMINATED POLYETHERS

    Institute of Scientific and Technical Information of China (English)

    YU Yunchao; LI Yiming

    1983-01-01

    Carboxyl terminated polyethers, the adducts of hydroxyl terminated polytetrahydrofuran and maleic anhydride, were used as toughener for epoxy resins. The morphology of the toughened resins was investigated by means of turbidity measurement, dynamic mechanical testing and scanning electron microscope observation. It turned out that the molecular weight and the carboxyl content of the polyether and the cure conditions are important factors, which affect the particle size of the polyether-rich domains and, in turn, the mechanical properties of the cured resin. Carboxyl terminated polytetrahydrofurans have a low glass transition temperature, and in appropriate amount they do not affect the thermal resistance of the resin. These advantages make them preferable as toughener for epoxy resins.

  3. Novel Polymers with Carboxylic Acid Loading

    DEFF Research Database (Denmark)

    Thomsen, Anders Daugaard; Malmström, Eva; Hvilsted, Søren

    2006-01-01

    Click chemistry has been used to prepare a range of novel polymers with pendant carboxylic acid side groups. Four azido carboxylic acids, either mono- or difunctional and aliphatic or aromatic, have been prepared and thoroughly characterized. Extensive model reactions with 1-ethyl-4-hydroxybenzene......, the simplest model for poly(4-hydroxystyrene), and the four azido carboxylic acids have been conducted to establish the proper reaction conditions and provide an analytical frame for the corresponding polymers. Poly(4-hydroxystyrene) moieties in three different polymers—poly(4-hydroxystyrene), poly(4...... the polymers in general exhibit [when poly(4-hydroxystyrene) is a substantial part] significant changes in the glass-transition temperature from the polar poly(4-hydroxystyrene) (120–130 °C) to the much less polar alkyne polymers (46–60 °C). A direct correlation between the nature of the pendant groups...

  4. Carboxylic acid reductase is a versatile enzyme for the conversion of fatty acids into fuels and chemical commodities.

    Science.gov (United States)

    Akhtar, M Kalim; Turner, Nicholas J; Jones, Patrik R

    2013-01-01

    Aliphatic hydrocarbons such as fatty alcohols and petroleum-derived alkanes have numerous applications in the chemical industry. In recent years, the renewable synthesis of aliphatic hydrocarbons has been made possible by engineering microbes to overaccumulate fatty acids. However, to generate end products with the desired physicochemical properties (e.g., fatty aldehydes, alkanes, and alcohols), further conversion of the fatty acid is necessary. A carboxylic acid reductase (CAR) from Mycobacterium marinum was found to convert a wide range of aliphatic fatty acids (C(6)-C(18)) into corresponding aldehydes. Together with the broad-substrate specificity of an aldehyde reductase or an aldehyde decarbonylase, the catalytic conversion of fatty acids to fatty alcohols (C(8)-C(16)) or fatty alkanes (C(7)-C(15)) was reconstituted in vitro. This concept was applied in vivo, in combination with a chain-length-specific thioesterase, to engineer Escherichia coli BL21(DE3) strains that were capable of synthesizing fatty alcohols and alkanes. A fatty alcohol titer exceeding 350 mg·L(-1) was obtained in minimal media supplemented with glucose. Moreover, by combining the CAR-dependent pathway with an exogenous fatty acid-generating lipase, natural oils (coconut oil, palm oil, and algal oil bodies) were enzymatically converted into fatty alcohols across a broad chain-length range (C(8)-C(18)). Together with complementing enzymes, the broad substrate specificity and kinetic characteristics of CAR opens the road for direct and tailored enzyme-catalyzed conversion of lipids into user-ready chemical commodities. PMID:23248280

  5. Online Measurement of the Intramolecular Isotopic Composition of Acetate in Natural Porewater Samples

    Science.gov (United States)

    Thomas, R. B.; Arthur, M. A.; Freeman, K. H.

    2006-12-01

    other volatile acids and water on a polar column (Nukol, Supelco). Following the GC, the acetic acid is reacted with either a combustion furnace (for total acetate) or a pyrolysis furnace for the carboxyl carbon only. The pyrolysis furnace operates at 600°C with Pd wire catalyst and a continuous trickle of H2. The resulting CO2 is then analyzed by conventional IRMS. This GC-PY-IRMS technique is coupled to a GC-C-IRMS such that switching between oxidation and pyrolysis is accomplished by a simple switch followed by a short stabilization period. The above pyrolysis conditions result in a small but characterizable oxidation of methyl carbon to CO2. The cross-contamination of acetate methyl into the acetate carboxyl signal is estimated to be approximately 15 to 20% of the IRMS signal and an isotope dilution series is used to estimate and correct for this contamination. Since this technique is online and allows for the injection of water samples the need for sample extraction and separation are eliminated. This method also significantly improves detection limits over the Dias 2002 method by avoiding SPME injections which have unfavorable partition coefficients for aqueous solutions of acetate.

  6. Mass spectrometric behaviour of carboxylated polyethylene glycols and carboxylated octylphenol ethoxylates.

    Science.gov (United States)

    Frańska, Magdalena; Zgoła, Agnieszka; Rychłowska, Joanna; Szymański, Andrzej; Łukaszewski, Zenon; Frański, Rafał

    2003-01-01

    Mass spectrometric behaviour of mono- and di-carboxylated polyethylene glycols (PEGCs and CPEGCs) and carboxylated octylphenol ethoxylates (OPECs) are discussed. The tendency for ionisation (deprotonation, protonation and cationisation by alkali metal cations) of carboxylated PEGs was compared with that of non-carboxylated correspondents by using both secondary ion mass spectrometry (SIMS) and electrospray ionisation (ESI). The fragmentation of the PEGCs and CPEGCs is discussed and also compared with their neutral correspondents, PEGs. The B/E mass spectra were recorded, using secondary ion mass spectrometry as a method for generation, for deprotonated and protonated molecules and molecules cationised by alkali metal cations. The fragmentation behaviour of PEGs is found to be different from that of CPEGCs, The presence of carboxylic groups may be confirmed not only by the determination of molecular weights of the ethoxylates studied, but also on the basis of the fragment ions formed. The metastable decomposition of the [OPEC-H](-) ions proceed through the cleavage of the bond between the octylphenol moiety and the ethoxylene chain leading to the octylphenoxy anions. It permits determination of the mass of the hydrophobic moiety of the studied carboxylated alkylphenol ethoxylate. ESI mass spectra recorded in the negative ion mode were found to be more suitable for the determination of the average molecular weight of carboxylated ethoxylates than SI mass spectra. PMID:12939494

  7. Radiation sterilization of hydrocortisone acetate

    International Nuclear Information System (INIS)

    The feasibility of using high energy ionizing radiation for the sterilization of hydrocortisone acetate was investigated. Hydrocortisone acetate in the form of powder was exposed to different dose levels of gamma radiation using a Cobalt-60 source. The irradiated samples were examined by various physico-chemical techniques in order to detect possible radiolysis products. It was of interest to know if one could insure sterility and retain biological properties of the drug by suitable choice of radiation dose. The results showed that a 10 KGy radiation dose causes no change in the physico-chemical properties of the drug and is sufficient to obtain contaminant-free product

  8. [Synthesis, structures, and acute toxicity of gossypol nonsymmetrical aldehyde derivatives].

    Science.gov (United States)

    Tiliabaev, K Z; Kamaev, F G; Vypova, N L; Iuldashev, A M; Ibragimov, B T; Talipov, S A

    2010-01-01

    Nonsymmetrical aldehyde derivatives of gossypol, a yellow polyphenolic pigment of cottonseed, were synthesized by reactions with ammonia, aniline, 4-aminoantipyrine, and barbituric acid. Their structures were determined by UV spectrophotometry and IR and (1)H NMR spectroscopy methods. Their acute toxicities in white mice were compared with those of gossypol and the corresponding symmetrical analogues. It was demonstrated that in general, the fewer free aldehyde groups that contained the gossypol derivative, the lower its acute toxicity. Only in the case of a nonsymmetrical gossypol derivative bearing a 4-aminoantipyrine residue did we observe a deviation from the above correlation: its symmetrical counterpart was even more toxic, but still less toxic than gossypol. PMID:20644599

  9. Structural and thermal properties of carboxylic acid functionalized polythiophenes

    Directory of Open Access Journals (Sweden)

    Ariane de França Mescoloto

    2014-01-01

    Full Text Available Polythiophenes functionalized with polar groups at the end of side-chain have emerged as an alternative method to obtain good compatibility between this class of conjugated polymers and electron acceptor compounds. The aim is to prevent phase segregation and to improve the efficiency of the polythiophene technological devices. However, homopolymers synthesized from thiophene rings with high polar groups at the end of the side-chain, such as hydroxyl and carboxylic acid groups, are poorly soluble in common volatile organic solvents. We report on a systematic preparation of copolymers of 3-hexylthiophene (HT and thiophene-3-acetic acid (TAA, using different feed ratios. The chemical structures of the copolymers were confirmed by FTIR and ¹H-NMR. The TAA content in these copolymers were 33, 38 and 54 mol %. HPSEC results did not show any remarkable correlation with TAA contents in the copolymers. In contrast, the thermal analyses showed a decrease in the thermal stability and an increase in rigidity of their backbones, for the copolymers with high amounts of TAA. The solubility and optical property of copolymers were also related to the TAA contents. Thus, the properties of these copolymers can be modulated by a simple control of feed ratio of TAA in the copolymerization.

  10. Prognostic values of aldehyde dehydrogenase 1 isoenzymes in ovarian cancer

    OpenAIRE

    Ma YM; Zhao S

    2016-01-01

    Yu-mei Ma,1 Shan Zhao2 1Department of Pathology, 2Department of Cancer Second Division, The Second Hospital of Hebei Medical University, Shijiazhuang City, People’s Republic of China Abstract: Aldehyde dehydrogenase 1 (ALDH1) activity has been used as a functional stem cell marker to isolate cancer stem cells in different cancer types, including ovarian cancer. However, which ALDH1’s isoenzymes are contributing to ALDH1 activity in ovarian cancer remains elusive. In addition, th...

  11. Characterization of the rat Class 3 aldehyde dehydrogenase gene promoter.

    OpenAIRE

    Xie, Y Q; Takimoto, K; Pitot, H. C.; Miskimins, W K; Lindahl, R

    1996-01-01

    The Class 3 aldehyde dehydrogenase gene (ALDH-3) is differentially expressed. Expression is either constitutive or xenobiotic inducible via an aromatic hydrocarbon (Ah) receptor-mediated pathway, depending upon the tissue. A series of studies were performed to examine the regulation of rat ALDH-3 basal expression. DNase I footprint analysis identified four DNA regions within the proximal 1 kb of the 5' flanking region of rat ALDH-3 which interact with regulatory proteins. Reporter gene and ge...

  12. An efficient and versatile synthesis of aromatic nitriles from aldehydes

    Institute of Scientific and Technical Information of China (English)

    Maryam Hajjami; Arash Ghorbani-Choghamarani; Mohammad Ali Zolfigol; Fatemeh Gholamian

    2012-01-01

    A simple and direct method has been developed for synthesis of nitriles based on one-pot reaction of aromatic aldehydes with three different kind of reagents:CeCl3·7H2O/KI/H2O2,CeCl3·7H2O/KI/UHP and (NH4)2Ce(NO3)6/KI/H2O2 in aqueous ammonia.

  13. Aldehyde dehydrogenase inhibition as a pathogenic mechanism in Parkinson disease

    OpenAIRE

    Fitzmaurice, Arthur G.; Rhodes, Shannon L.; Lulla, Aaron; Murphy, Niall P.; Lam, Hoa A.; O’Donnell, Kelley C.; Barnhill, Lisa; Casida, John E.; Cockburn, Myles; Sagasti, Alvaro; Stahl, Mark C.; Maidment, Nigel T; Ritz, Beate; Bronstein, Jeff. M.

    2013-01-01

    Parkinson disease (PD) is a neurodegenerative disorder particularly characterized by the loss of dopaminergic neurons in the substantia nigra. Pesticide exposure has been associated with PD occurrence, and we previously reported that the fungicide benomyl interferes with several cellular processes potentially relevant to PD pathogenesis. Here we propose that benomyl, via its bioactivated thiocarbamate sulfoxide metabolite, inhibits aldehyde dehydrogenase (ALDH), leading to accumulation of the...

  14. Nitric Acid Dehydration Using Perfluoro Carboxylate and Mixed Sulfonate/Carboxylate Membranes

    Energy Technology Data Exchange (ETDEWEB)

    R.L. Ames

    2004-09-01

    Perfluoro ionomer membranes are tetrafluoro ethylene-based materials with microheterogeneous structures consisting of a hydrophobic polymer backbone and a hydrophilic side-chain cluster region. Due to the ionomer cluster morphology, these films exhibit unique transport properties. Recent investigations with perfluoro sulfonate and perfluoro sulfonate/carboxylate composite polymers have demonstrated their value in the dehydration of nitric acid and they show potential as an alternative to conventional, energy intensive unit operations in the concentration of acid feeds. As a result, investigations were conducted to determine the feasibility of using pure perfluoro carboxylate and mixed perfluoro sulfonate/carboxylate films for the dehydration of nitric acid because of the speculation of improved water selectivity of the carboxylate pendant chain. During the first phase of these investigations the effort was focused on generating a thin, solution cast perfluoro carboxylate ionomer film, to evaluate the general, chemical and physical characteristics of the polymer, and to assess the material's aqueous transport performance (flux and nitrate separation efficiencies) in pervaporation and high-pressure environments. Results demonstrated that generating robust solution-cast films was difficult yet a number of membranes survived high trans-membrane pressures up to 700 psig. General characterization of the solution cast product showed reduced ion exchange capacities when compared with thicker, ''as received'' perfluoro carboxylate and similar sulfonate films. Small angle x-ray scattering analysis results suggested that the solution cast carboxylate films contained a small fraction of sulfonate terminated side-chains. Aqueous transport experimentation showed that permeate fluxes for both pure water and nitric acid were approximately two orders of magnitude smaller for the carboxylate solution cast membranes when compared to their sulfonate

  15. γ-Unsaturated aldehydes as potential Lilial replacers.

    Science.gov (United States)

    Schroeder, Martin; Mathys, Marion; Ehrensperger, Nadja; Büchel, Michelle

    2014-10-01

    A series of Claisen rearrangements was undertaken in order to find a replacement for Lilial (=3-(4-(tert-butyl)phenyl)-2-methylpropanal), a high-tonnage perfumery ingredient with a lily-of-the-valley odour, which is a CMR2 material [1]. 5,7,7-Trimethyl-4-methyleneoctanal (10), the synthesis of which is described, became the main lead. It possesses an odour which is very close to that of Lilial but lacks its substantivity. Aldehydes with higher molecular weights than that of 10 were, therefore, synthesised in order to boost substantivity and to understand the structural requirements for a 'Lilial' odour. The aldehydes were obtained via Claisen rearrangements of 'exo-methylidene' vinyl ethers, allenyl vinyl ethers, or allenyl allyl ethers. Alternatively, coupling of terminal alkynes with allyl alcohols led to the desired aldehydes. Derivatives of 10 and their sila analogues were also synthesised. The olfactory properties of all synthesised molecules were evaluated for possible structure-odour relationships (SOR). PMID:25329790

  16. Methyl 3-(Quinolin-2-ylindolizine-1-carboxylate

    Directory of Open Access Journals (Sweden)

    Roumaissa Belguedj

    2015-12-01

    Full Text Available A novel compound, methyl 3-(quinolin-2-ylindolizine-1-carboxylate (2 has been synthesized by cycloaddition reaction of 1-(quinolin-2-ylmethylpyridinium ylide (1 with methyl propiolate in presence of sodium hydride in THF. The structure of this compound was established by IR, 1H-NMR, 13C-NMR and MS data

  17. 2-Isopropyl-5-methylcyclohexyl quinoline-2-carboxylate

    Directory of Open Access Journals (Sweden)

    E. Fazal

    2014-01-01

    Full Text Available In the title compound, C20H25NO2, the cyclohexyl ring adopts a slightly disordered chair conformation. The dihedral angle between the mean planes of the quinoline ring and the carboxylate group is 22.2 (6°. In the crystal, weak C—H...N interactions make chains along [010].

  18. Antibiofilm Properties of Acetic Acid

    DEFF Research Database (Denmark)

    Bjarnsholt, Thomas; Alhede, Morten; Jensen, Peter Østrup;

    2014-01-01

    infected implant, tissue, or organ and thereby the biofilm. Acetic acid is known for its antimicrobial effect on bacteria in general, but has never been thoroughly tested for its efficacy against bacterial biofilms. In this article, we describe complete eradication of both Gram-positive and Gram...

  19. The FEMA GRAS assessment of phenethyl alcohol, aldehyde, acid, and related acetals and esters used as flavor ingredients

    NARCIS (Netherlands)

    Adams, T.B.; Cohen, S.M.; Doull, J.; Feron, V.J.; Goodman, J.I.; Marnett, L.J.; Munro, I.C.; Portoghese, P.S.; Smith, R.L.; Waddell, W.J.; Wagner, B.M.

    2005-01-01

    This publication is the ninth in a series of safety evaluations performed by the Expert Panel of the Flavor and Extract Manufacturers Association (FEMA). In 1993, the Panel initiated a comprehensive program to re-evaluate the safety of more than 1700 GRAS flavoring substances under conditions of int

  20. GRE2 from Scheffersomyces stipitis as an aldehyde reductase contributes tolerance to aldehyde inhibitors derived from lignocellulosic biomass.

    Science.gov (United States)

    Wang, Xu; Ma, Menggen; Liu, Z Lewis; Xiang, Quanju; Li, Xi; Liu, Na; Zhang, Xiaoping

    2016-08-01

    Scheffersomyces (Pichia) stipitis is one of the most promising yeasts for industrial bioethanol production from lignocellulosic biomass. S. stipitis is able to in situ detoxify aldehyde inhibitors (such as furfural and 5-hydroxymethylfurfural (HMF)) to less toxic corresponding alcohols. However, the reduction enzymes involved in this reaction remain largely unknown. In this study, we reported that an uncharacterized open reading frame PICST_72153 (putative GRE2) from S. stipitis was highly induced in response to furfural and HMF stresses. Overexpression of this gene in Saccharomyces cerevisiae improved yeast tolerance to furfural and HMF. GRE2 was identified as an aldehyde reductase which can reduce furfural to FM with either NADH or NADPH as the co-factor and reduce HMF to FDM with NADPH as the co-factor. This enzyme can also reduce multiple aldehydes to their corresponding alcohols. Amino acid sequence analysis indicated that it is a member of the subclass "intermediate" of the short-chain dehydrogenase/reductase (SDR) superfamily. Although GRE2 from S. stipitis is similar to GRE2 from S. cerevisiae in a three-dimensional structure, some differences were predicted. GRE2 from S. stipitis forms loops at D133-E137 and T143-N145 locations with two α-helices at E154-K157 and E252-A254 locations, different GRE2 from S. cerevisiae with an α-helix at D133-E137 and a β-sheet at T143-N145 locations, and two loops at E154-K157 and E252-A254 locations. This research provided guidelines for the study of other SDR enzymes from S. stipitis and other yeasts on tolerant mechanisms to aldehyde inhibitors derived from lignocellulosic biomass. PMID:27003269

  1. In vitro assessment of human airway toxicity from major aldehydes in automotive emissions

    Energy Technology Data Exchange (ETDEWEB)

    Grafstroem, R.C. [Karolinska Inst., Stockholm (Sweden). Inst. of Environmental Medicine

    1997-09-01

    Automotive exhausts can significantly contribute to the levels of reactive aldehydes, including formaldehyde, acetaldehyde and acrolein, in urban air. The use of alcohols as an alternative fuel for gasoline or diesel may further increase these emissions. Since it is unclear if aldehyde inhalation may induce pathological states, including cancer, in human airways, the toxic properties of the above-mentioned aldehydes were studied in cultured target cell types. Each aldehyde modified vital cellular functions in a dose-dependent manner, and invariably inhibited growth and induced abnormal terminal differentiation. Decreases of cellular thiols and increases of intracellular Ca{sup 2+} were observed, and moreover, variable types and amounts of short-lived or persistent genetic damage were induced. The concentrations required for specified levels of a particular type of injury varied up to 10000-fold among the aldehydes. Overall, distinctive patterns of cytopathological activity were observed, which differed both qualitatively and quantitatively among the aldehydes. Finally, aldehydes inhibited DNA repair processes and increased cytotoxicity and mutagenesis in synergy with other known toxicants, indicating that aldehydes may also enhance damage by other constituents in automotive exhausts. In summary, the aldehydes, notably {sup m}u{sup M}-mM formaldehyde, caused pathological effects and induced mechanisms that relate to acute toxicity and cancer development in airway epithelial cells. Since `no-effect` levels may not exist for carcinogenic agents, the overall results support a need for elimination of aldehydes in automotive exhausts. 41 refs

  2. Solution-processable carboxylate-capped CuO nanoparticles obtained by a simple solventless method

    International Nuclear Information System (INIS)

    Carboxylate-capped CuO nanoparticles were obtained via a simple solventless route, based on the thermal decomposition at 120 °C of solid precursors. The reaction mixture consisted of copper acetate monohydrate, acting as the CuO precursor, and different organic carboxylic acids (lauric, phenylvaleric or 3,6,9-trioxadecanoic acid) used as the capping agent. The proposed method, in good agreement with environmentally friendly practices, produced dry nanoparticles, thereby totally eliminating the need of washing, filtration, or other downstream steps. Transmission electron micrographs show crystalline roughly spherical CuO nanoparticles with average diameters between 3.1 and 5.5 nm depending on the capping ligand. The laurate-capped CuO nanoparticles showed a paramagnetic behaviour at room temperature, while a weak ferromagnetic component was detected at low temperature (<40 K). It was also proved that the chemical structure of the carboxylic acid tail enabled the straightforward dispersibility of nanoparticles in common solvents and assisted in the deposition of the material as thin films.

  3. Glycerol acetals, kinetic study of the reaction between glycerol and formaldehyde

    International Nuclear Information System (INIS)

    The acetalization reaction between glycerol and formaldehyde using Amberlyst 47 acidic ion exchange resin was studied. These acetals can be obtained from renewable sources (bioalcohols and bioalcohol derived aldehydes) and seem to be good candidates for different applications such as oxygenated diesel additives. A preliminary kinetic study was performed in a batch stirred tank reactor studying the influence of different process parameters like temperature, feed composition and the stirring speed. A pseudo homogenous kinetic model able to explain the reaction mechanism was adjusted. Thus, the corresponding order of reaction was determined. Amberlyst 47 acidic ion exchange resin showed a fairly good behavior allowing 100% of selectivity towards acetals formation. However, the studied acetalization reaction showed high thermodynamic limitations achieving glycerol conversions around 50% using a stoichiometric feed ratio at 353 K. The product is a mixture of two isomers (1,3-Dioxan-5-ol and 1,3-dioxolane-4-methanol) and the conversion of 1,3-dioxolane-4-methanol into 1,3-Dioxan-5-ol was also observed. -- Highlights: → The reaction between glycerol and acetaldehyde shows thermodynamic limitations. → Amberlyst 47 ion exchange resins show 100% of selectivity. → A pseudo-homogeneous kinetic model is able to predict the reaction progress. → Isomerization reactions were observed from dioxalanes to dioxanes.

  4. Production of carboxylic acid and salt co-products

    Energy Technology Data Exchange (ETDEWEB)

    Hanchar, Robert J.; Kleff, Susanne; Guettler, Michael V.

    2014-09-09

    This invention provide processes for producing carboxylic acid product, along with useful salts. The carboxylic acid product that is produced according to this invention is preferably a C.sub.2-C.sub.12 carboxylic acid. Among the salts produced in the process of the invention are ammonium salts.

  5. 40 CFR 721.2950 - Carboxylic acid glycidyl esters.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Carboxylic acid glycidyl esters. 721... Substances § 721.2950 Carboxylic acid glycidyl esters. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as carboxylic acid glycidyl...

  6. Scalar Relativistic Study of the Structure of Rhodium Acetate

    Directory of Open Access Journals (Sweden)

    Emily E. Edwards

    2004-01-01

    Full Text Available Abstract: Rhodium acetate, related rhodium carboxylates, and rhodium amide complexes are powerful catalysts for carbene chemistry. They readily promote the decomposition of diazo compounds and transfer the resulting carbene to a variety of substrates. There have been several quantum chemistry studies of these compounds, particularly of the acetate. These have all used non-relativistic methods, and all have shown optimized Rh-Rh bond lengths significantly longer than the experimental value. In this study we have surveyed several scalar relativistic DFT methods using Gaussian, Slater, and numerical basis functions (in DGAUSS, ADF, and DMOL3. Several combinations of exchange-correlation functionals with relativistic and non-relativistic effective core potentials (ECP were investigated, as were non-relativistic and all electron scalar relativistic methods. The combination of the PW91 exchange and PW91 correlation functional with the Christiansen-Ermler ECP gave the best results: 2.3918 Å compared to the experimental value of 2.3855±0.0005 Å.

  7. Inoculum characterization: identification of acetate consumption routes

    OpenAIRE

    García Ruiz, Javier; Flotats Ripoll, Xavier; Tey, Laura; Fernández García, Belén

    2015-01-01

    A mesophilic inoculum, likely to have syntrophic acetate oxidation bacteria (SAOB) and hydrogenotrophic methanogen (HM) activity due to operational conditions, was characterized by means of methanogenic activity tests, submitting it to different acetate and ammonia nitrogen (TAN) concentrations.

  8. Expression, crystallization and preliminary X-ray crystallographic analysis of aldehyde dehydrogenase (ALDH) from Bacillus cereus

    International Nuclear Information System (INIS)

    Aldehyde dehydrogenase (ALDH) catalyses the oxidation of aldehydes using NAD(P)+ as a cofactor. The aldh gene from B. cereus was cloned; the protein was expressed, purified and crystallized, and a preliminary X-ray crystallography analysis was performed. Aldehyde dehydrogenase (ALDH) catalyses the oxidation of aldehydes using NAD(P)+ as a cofactor. Most aldehydes are toxic at low levels. ALDHs are used to regulate metabolic intermediate aldehydes. The aldh gene from Bacillus cereus was cloned and the ALDH protein was expressed, purified and crystallized. A crystal of the ALDH protein diffracted to 2.6 Å resolution and belonged to the monoclinic space group P21, with unit-cell parameters a = 83.5, b = 93.3, c = 145.5 Å, β = 98.05°. Four protomers were present in the asymmetric unit, with a corresponding VM of 2.55 Å3 Da−1 and a solvent content of 51.8%

  9. Acetate reduces microglia inflammatory signaling in vitro

    OpenAIRE

    Soliman, Mahmoud L; Puig, Kendra L.; Combs, Colin K.; Rosenberger, Thad A.

    2012-01-01

    Acetate supplementation increases brain acetyl-CoA and histone acetylation and reduces lipopolysaccharide (LPS)-induced neuroglial activation and interleukin (IL)-1β expression in vivo. To determine how acetate imparts these properties, we tested the hypothesis that acetate metabolism reduces inflammatory signaling in microglia. To test this, we measured the effect acetate treatment had on cytokine expression, mitogen-activated protein kinase (MAPK) signaling, histone H3 at lysine 9 acetylati...

  10. Importance of secondary sources in the atmospheric budgets of formic and acetic acids

    Directory of Open Access Journals (Sweden)

    F. Paulot

    2010-10-01

    Full Text Available We present a detailed budget of formic and acetic acids, two of the most abundant trace gases in the atmosphere. Our bottom-up estimate of the global source of formic and acetic acids are ~1200 and ~1400 Gmol/yr, dominated by photochemical oxidation of biogenic volatile organic compounds, in particular isoprene. Their sinks are dominated by wet and dry deposition. We use the GEOS-Chem chemical transport model to evaluate this budget against an extensive suite of measurements from ground, ship and satellite-based Fourier transform spectrometers, as well as from several aircraft campaigns over North America. The model captures the seasonality of formic and acetic acids well but generally underestimates their concentration, particularly in the Northern midlatitudes. We infer that the source of both carboxylic acids may be up to 50% greater than our estimate and report evidence for a long-lived missing secondary source of carboxylic acids that may be associated with the aging of organic aerosols. Vertical profiles of formic acid in the upper troposphere support a negative temperature dependence of the reaction between formic acid and the hydroxyl radical as suggested by several theoretical studies.

  11. Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling

    Science.gov (United States)

    Duncan, Kyle D.; Volmer, Dietrich A.; Gill, Chris G.; Krogh, Erik T.

    2016-03-01

    Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H]-) ions with limited selective fragmentation. However, carboxylates cationized with Ba2+ have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba]+ precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH]+ and [BaOH]+). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

  12. Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling.

    Science.gov (United States)

    Duncan, Kyle D; Volmer, Dietrich A; Gill, Chris G; Krogh, Erik T

    2016-03-01

    Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H](-)) ions with limited selective fragmentation. However, carboxylates cationized with Ba(2+) have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba](+) precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH](+) and [BaOH](+)). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization. PMID:26689207

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

    OpenAIRE

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

    2013-01-01

    Aldehydes are generated by oxidized lipids and carbohydrates at increased levels under conditions of metabolic imbalance and oxidative stress during atherosclerosis, myocardial and cerebral ischemia, diabetes, neurodegenerative diseases and trauma. In most tissues, aldehydes are detoxified by oxidoreductases that catalyze the oxidation or the reduction of aldehydes or enzymatic and nonenzymatic conjugation with low molecular weight thiols and amines, such as glutathione and histidine dipeptid...

  14. Research advances in the catalysts for the selective oxidation of ethane to aldehydes

    Institute of Scientific and Technical Information of China (English)

    ZHANG Zhe; ZHAO Zhen; XU Chunming

    2005-01-01

    Selective oxidation of ethane to aldehydes is one of the most difficult processes in the catalysis researches of low alkanes. The development of selective oxidation of ethane to aldehydes (formaldehyde, acetaldehyde and acrolein) is discussed. The latest progress of the catalysts, including bulk or supported metal oxide catalysts, highly dispersed and isolated active sites catalysts, and the photo-catalytic ethane oxidation catalysts, partial oxidation of ethane in the gas phase, and the proposed reaction pathways from ethane to aldehydes are involved.

  15. Polyphenolic acetates : A newer anti-Mycobacterial therapeutic option

    Directory of Open Access Journals (Sweden)

    Santram

    2014-01-01

    Full Text Available The objective of our research project was screening of various highly specific substrates of Acetoxy Drug: Protein Transacytylase (M.TAase for antimycobacterial activity. Mycobacterial culture was done in Middlebrook’s 7H9 media. Protein purification (Mycobacterial Tranacetylase, M.TAase was done by ion exchange chromatography and its demonstration was done on SDS- polyacrylamide gel electrophoresis (SDS-PAGE and western blot. Middlebrook’s 7H9 broth was procured from Becton Dickinson. CM-Sepharose, DEAE-Sepharose and Q-Sephharose were purchased from Amersham Pharmacia. Anti acetyl lysine polyclonal antibody was purchased from Cell Signaling. The Middlebrook 7H9 medium was used for M. smegmatis culture. The media was prepared according to the manufacturer’s instructions. The various Polyphenol acetate compounds were tested for their antimycobacterial activities. Minimal inhibitory concentrations (MIC were calculated by Alamar blue dye assay method. The GST protein was used as a receptor protein and purified Mycobacterial Glutamine Synthetase (GS as TAase for acetylation by DAMC. To demonstrate the TAase catalyzed acetylation of GST by DAMC, purified M.TAase (GS was preincubated with GST and DAMC followed by western blot using anti acetyl lysine antibody, which avidly react with the acetylated proteins. The growth pattern of M. smegmatis was diminished under the influence of various polyphenolic acetates (PA tested for their anti-mycobacterial activity. DAMC and DAMC-5-carboxylic acid was found to have MIC of 40μg/ml whereas DAMC-6-carboxylic acid was reported to have MIC value of 35μg/ml and for ellagic acid tetra acetate (EATA it was 60μg/ml. Previous work in our lab has led to discovery of a novel enzyme acetoxy drug: protein transacetylase (TAase, catalyzing transfer of acetyl group from various polyphenolic peracetate (PA to certain receptor proteins such as cytochromes P-450, NADPH cytochrome reductase, nitric oxide synthase (NOS

  16. Pallidol hexaacetate ethyl acetate monosolvate

    Directory of Open Access Journals (Sweden)

    Qinyong Mao

    2013-07-01

    Full Text Available The entire molecule of pallidol hexaacetate {systematic name: (±-(4bR,5R,9bR,10R-5,10-bis[4-(acetyloxyphenyl]-4b,5,9b,10-tetrahydroindeno[2,1-a]indene-1,3,6,8-tetrayl tetraacetate} is completed by the application of twofold rotational symmetry in the title ethyl acetate solvate, C40H34O12·C4H8O2. The ethyl acetate molecule was highly disordered and was treated with the SQUEEZE routine [Spek (2009. Acta Cryst. D65, 148–155]; the crystallographic data take into account the presence of the solvent. In pallidol hexaacetate, the dihedral angle between the fused five-membered rings (r.m.s. deviation = 0.100 Å is 54.73 (6°, indicating a significant fold in the molecule. Significant twists between residues are also evident as seen in the dihedral angle of 80.70 (5° between the five-membered ring and the pendent benzene ring to which it is attached. Similarly, the acetate residues are twisted with respect to the benzene ring to which they are attached [C—O(carboxy—C—C torsion angles = −70.24 (14, −114.43 (10 and −72.54 (13°]. In the crystal, a three-dimensional architecture is sustained by C—H...O interactions which encompass channels in which the disordered ethyl acetate molecules reside.

  17. Acet-oxy-γ-valerolactone.

    Science.gov (United States)

    Tristram, Cameron; Gainsford, Graeme J; Hinkley, Simon

    2013-06-01

    Levulinyl cellulose esters have been produced as an effective renewable binder for architectural coatings. The title compound, C7H10O4 (systematic name: 2-methyl-5-oxo-tetra-hydro-furan-2-yl acetate), assigned as the esterifying species, was isolated and crystallized to confirm the structure. In the crystal, the mol-ecules pack in layers parallel to (102) utilizing weak C-H⋯O inter-actions. PMID:23795112

  18. Determination of the thermodynamic quantities of complexation between Eu(III) and carboxylic acids by microcalorimetry

    International Nuclear Information System (INIS)

    Potentiometric and microcalorimetric titration techniques were applied to determine the Gibbs free energies and enthalpies of the protonation of some carboxylic acids (acetic, glycolic, malonic and malic acids) and their complexation with Eu(III) in 1.0 M NaClO4 solution at 25 C, where Eu(III) was used as a chemical analogue of radiologically important Am(III). By using the values of ΔG determined by potentiometric titrations, the results of calorimetric titrations were analyzed to give the values of ΔH and ΔS. To support the discussion on the obtained thermodynamic quantities, the hydration numbers of Eu(III) in the complexes were obtained by TRLFS measurement, where the luminescence lifetime of Eu(III) excited by 394 nm laser was measured. A few to several kJ/mol of enthalpies were determined for the reactions within the uncertainties of ±0.01 to ±0.4. These enthalpy values indicated that the protonation of these carboxylates were entropy-driven, that is, vertical stroke - TΔS vertical stroke >> vertical stroke ΔH vertical stroke in ΔG = ΔH - TΔS. The complexations of Eu(III) were also shown to be controlled mainly by entropy term. The results of TRLFS measurement revealed that the number of dehydrated water molecule increased with the degree of complexation. A linear relation was found between total entropy change of the system (ΔST) and the net number of released molecules from the central Eu(III) ion. However, the values of ΔST for the hydroxy-carboxylates were smaller than that for simple carboxylates at the same net number of molecules released from Eu(III), suggesting that the dehydration occurred not only in the cation but also in the anion. (orig.)

  19. Carboxylated Polyurethanes Containing Hyperbranched Polyester Soft Segments

    Directory of Open Access Journals (Sweden)

    Žigon, M.

    2006-09-01

    Full Text Available hyperbranched polyester soft segments (HB PU with functional carboxylic groups in order to enable the preparation of stable HB PU dispersions. Carboxylated hyperbranched polyurethanes were synthesized using a hyperbranched polyester based on 2,2-bis(methylolpropionic acid of the fourth pseudo-generation (Boltorn H40 and hexamethylene (HDI or isophorone diisocyanate (IPDI. The reactivity of hyperbranched polyester with HDI was lower than expected, possibly due to the presence of less reactive hydroxyl groups in the linear repeat units. A gel was formed at mole ratios rNCO/OH = 1:2 or 1:4. The synthesis of HB PU was performed with partly esterified hyperbranched polyester with lowered hydroxyl functionality. The carboxyl groups were incorporated in the HB PU backbone by reaction of residual hydroxyl groups with cis-1,2-cyclohexanedicarboxylic anhydride. HB PU aqueous dispersions were stable at least for two months, although their films were brittle. The tensile strength and Young's modulus of blends of linear and HB PU decreased with increasing content of HB PU whereas elongation at break remained nearly constant, which was explained in terms of looser chain packing due to more open tree-like hyperbranched structures.

  20. Microwave Assisted Solvent Free Synthesis of Azomethines from Aryl Aldehydes on Melamin Formaldehyde as Solid Support

    OpenAIRE

    Ramin Rezaei; Mohammadi, Mohammad K; Tahereh Ranjbar

    2011-01-01

    Various aryl aldehydes underwent prompt one pot conversion into the corresponding azomethines in high yields by reacting with hydroxylamine hydrochloride supported on melamine formaldehyde under microwave irradiation.

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

    Science.gov (United States)

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

    2015-08-01

    Aldehydes and ketones compounds, as one of the components in the exhaust of restaurants, are a class of volatile organic compounds (VOCs) with strong chemical reactivity. However, there is no systematic study on aldehydes and ketones compounds in the exhaust of restaurants. To further clarify the food source emission levels of aldehydes and ketones compounds and controlling measures, to access city group catering VOCs emissions control decision-making basis, this study selected 8 Beijing restaurants with different types. The aldehydes and ketones compounds were sampled using DNPH-silica tube, and then ultra performance liquid chromatography was used for quantitative measurement. The aldehydes and ketones concentrations of reference volume condition from 8 restaurants in descending order were Roasted Duck restaurant, Chinese Style Barbecue, Home Dishes, Western Fast-food, School Canteen, Chinese Style Fast-food, Sichuan Cuisine, Huaiyang Cuisine. The results showed that the range of aldehydes and ketones compounds (C1-C9) concentrations of reference volume condition in the exhaust of restaurants was 115.47-1035.99 microg x m(-3). The composition of aldehydes and ketones compounds in the exhaust of sampled restaurants was obviously different. The percentages of C1-C3 were above 40% in the exhaust from Chinese style restaurants. Fast food might emit more C4-C9 aldehydes and ketones compounds. From the current situation of existing aldehydes and ketones compounds control, the removal efficiency of high voltage electrostatic purifiers widely used in Beijing is limited. PMID:26591999

  2. Monolayer structures of alkyl aldehydes: Odd-membered homologues

    OpenAIRE

    Phillips, T. K.; Clarke, Stuart M.; Castro Arroyo, Miguel Ángel; Millán, Carmen; Medina, Santiago

    2011-01-01

    Crystalline monolayers of three aldehydes with an odd number of carbon atoms in the alkyl chain (C 7, C 9 and C 11) at low coverages are observed by a combination of X-ray and neutron diffraction. Analysis of the diffraction data is discussed and possible monolayer crystal structures are proposed; although unique structures could not be ascertained for all molecules. We conclude that the structures are flat on the surface, with the molecules lying in the plane of the layer. The C 11 homologue...

  3. Monolayer structures of alkyl aldehydes: Odd-membered homologues

    International Nuclear Information System (INIS)

    Crystalline monolayers of three aldehydes with an odd number of carbon atoms in the alkyl chain (C7, C9 and C11) at low coverages are observed by a combination of X-ray and neutron diffraction. Analysis of the diffraction data is discussed and possible monolayer crystal structures are proposed; although unique structures could not be ascertained for all molecules. We conclude that the structures are flat on the surface, with the molecules lying in the plane of the layer. The C11 homologue is determined to have a plane group of either p2, pgb or pgg, and for the C7 homologue the p2 plane group is preferred.

  4. Piperidine Promoted Regioselective Synthesis of α, β-unsaturated Aldehydes

    Directory of Open Access Journals (Sweden)

    *A. H. Banday

    2013-03-01

    Full Text Available An efficient, facile and regioselective synthesis of α,β-unsaturated aldehydes from β-hydroxynitriles is reported. The reaction is carried out using DIBAL-H and promoted by piperidine under dry conditions at a temperature of -78 oC and can be described as a concomitant reduction-elimination reaction. The same reaction if carried out in the absence of piperidine gives mainly the uneliminated reduction product. The products formed are of immense importance as synthons in a large number of chemical reactions and biological processes.

  5. Piperidine Promoted Regioselective Synthesis of α, β-unsaturated Aldehydes

    OpenAIRE

    *A. H. Banday

    2013-01-01

    An efficient, facile and regioselective synthesis of α,β-unsaturated aldehydes from β-hydroxynitriles is reported. The reaction is carried out using DIBAL-H and promoted by piperidine under dry conditions at a temperature of -78 oC and can be described as a concomitant reduction-elimination reaction. The same reaction if carried out in the absence of piperidine gives mainly the uneliminated reduction product. The products formed are of immense importance as synthons in a large number of chemi...

  6. DNA-Templated Introduction of an Aldehyde Handle in Proteins

    DEFF Research Database (Denmark)

    Gothelf, Kurt Vesterager; Kodal, Anne Louise Bank; Mortensen, Michael Rosholm; Rosen, Christian Bech; Tørring, Thomas

    2016-01-01

    Many medical and biotechnological applications rely on labeling of proteins, but one key challenge is the production of homogeneous and site-specific conjugates. This can rarely be achieved by mere residue-specific random labeling, but requires genetic engineering. Using site-selective DNA......-binding site. Here, we demonstrate DNA-templated reductive amination for His6-tagged proteins and native metal-binding proteins, including IgG1 antibodies. We also use a cleavable linker between the DNA and the protein to remove the DNA and introduce a single aldehyde to proteins. This functions as a handle...

  7. Nuclear alkylated pyridine aldehyde polymers and conductive compositions thereof

    Science.gov (United States)

    Rembaum, A.; Singer, S. (Inventor)

    1970-01-01

    A thermally stable, relatively conductive polymer was disclosed. The polymer was synthesized by condensing in the presence of catalyst a 2, 4, or 6 nuclear alklylated 2, 3, or 4 pyridine aldehyde or quaternary derivatives thereof to form a polymer. The pyridine groups were liked by olefinic groups between 2-4, 2-6, 2-3, 3-4, 3-6 or 4-6 positions. Conductive compositions were prepared by dissolving the quaternary polymer and an organic charge transfer complexing agent such as TCNQ in a mutual solvent such as methanol.

  8. Coordination polymers of La(III) acetate with terephthalaldehyde bis isonicotinic acid hydrazone (Paper No. AL-12)

    International Nuclear Information System (INIS)

    Polymerization reactions involving the formation of schiff base metal complexes by condensation have been described. Metal complexes of schiff bases of hyrazides with aldehydes and ketones have been of special interest in recent years, particularly in the context of therapeutic value of hydrazide and hydrazone. The coordination occurs both in keto as well as in enolic form of ligands with metal ions. Coordination polymers of 3-d series have been extensively studied but less attention has been paid on rare earths polymeric complexes. The synthesis and characterization of lanthanide (La, Pr, Nd, Sr and Gd) acetate complexes with a schiff base derived from terephthalaldehyde and isonicotinic acidhydrazide are reported. (author)

  9. Surface chemical properties of sodium salts of carboxylic acids isolated from Green River shale. [Sodium carboxylates

    Energy Technology Data Exchange (ETDEWEB)

    McKay, J.F.; Blanche, M.S.; Robertson, R.E.

    1985-12-01

    Organic material isolated from Green River shale varies substantially with the method of isolation. Short-time supercritical fluid treatment and solvent extraction of Green River shale produces large amounts of sodium carboxylates. These sodium salts were observed to form emulsions and therefore be surface active. Quantitative surface activity measurements were then determined using the shale extract. The material was found to have a limiting surface tension of about 41 dynes/cm (as expected) for carboxylates. However, the critical micelle concentration is quite high and has a measured molecular weight value of 600. This probably results from higher solubility of the lower molecular weight species. The solution did not display hysteresis. In general the carboxylic acid salts isolated from Green River shale displayed surface activity similar to those of model compounds cited in the literature.

  10. Toxic Diatom Aldehydes Affect Defence Gene Networks in Sea Urchins

    Science.gov (United States)

    Varrella, Stefano; Ruocco, Nadia; Ianora, Adrianna; Bentley, Matt G.; Costantini, Maria

    2016-01-01

    Marine organisms possess a series of cellular strategies to counteract the negative effects of toxic compounds, including the massive reorganization of gene expression networks. Here we report the modulated dose-dependent response of activated genes by diatom polyunsaturated aldehydes (PUAs) in the sea urchin Paracentrotus lividus. PUAs are secondary metabolites deriving from the oxidation of fatty acids, inducing deleterious effects on the reproduction and development of planktonic and benthic organisms that feed on these unicellular algae and with anti-cancer activity. Our previous results showed that PUAs target several genes, implicated in different functional processes in this sea urchin. Using interactomic Ingenuity Pathway Analysis we now show that the genes targeted by PUAs are correlated with four HUB genes, NF-κB, p53, δ-2-catenin and HIF1A, which have not been previously reported for P. lividus. We propose a working model describing hypothetical pathways potentially involved in toxic aldehyde stress response in sea urchins. This represents the first report on gene networks affected by PUAs, opening new perspectives in understanding the cellular mechanisms underlying the response of benthic organisms to diatom exposure. PMID:26914213

  11. Radon and aldehyde concentrations in the indoor environment. Final report

    International Nuclear Information System (INIS)

    Findings regarding indoor air contaminants in the energy-efficient residence (EER) in Mt. Airy, Maryland are reported. The objectives of the study were to collect and analyze relevant air quality samples (specifically radon and aldehydes), characterize the indoor air quality with respect to radon and aldehydes, and develop relationships between air infiltration rates and contaminant levels. One-fifth of the measured formaldehyde concentrations were in the range that may cause health concerns. Although indoor temperature and relative humidity affect indoor HCHO concentration, the elevated formaldehyde concentrations were measured under very low air infiltration rates. The data show that ventilation of the indoor air space is somewhat effective in reducing high HCHO concentrations. The operation of the heat exchanger led to an increase of the air infiltration rate which in turn resulted in substantial reduction of formaldehyde concentrations. A considerable number of the collected samples of indoor air displayed radon concentrations at levels higher than 1.0 to 4.0 nCim-3 (assuming an equilibrium factor of 0.5, these radon levels would correspond to working levels above the health guidelines suggested by the US EPA for homes in Florida built on land reclaimed from phosphate mining). As in the case of indoor formaldehyde concentrations, elevated indoor concentrations are substantially reduced when the infiltration rate is increased. The data base shows that the use of the air to air heat exchanger leads to reduction of indoor radon concentration by increasing the residential ventilation rate

  12. Recovery of carboxylic acids produced during dark fermentation of food waste by adsorption on Amberlite IRA-67 and activated carbon.

    Science.gov (United States)

    Yousuf, Ahasa; Bonk, Fabian; Bastidas-Oyanedel, Juan-Rodrigo; Schmidt, Jens Ejbye

    2016-10-01

    Amberlite IRA-67 and activated carbon were tested as promising candidates for carboxylic acid recovery by adsorption. Dark fermentation was performed without pH control and without addition of external inoculum at 37°C in batch mode. Lactic, acetic and butyric acids, were obtained, after 7days of fermentation. The maximum acid removal, 74%, from the Amberlite IRA-67 and 63% from activated carbon was obtained from clarified fermentation broth using 200gadsorbent/Lbroth at pH 3.3. The pH has significant effect and pH below the carboxylic acids pKa showed to be beneficial for both the adsorbents. The un-controlled pH fermentation creates acidic environment, aiding in adsorption by eliminating use of chemicals for efficient removal. This study proposes simple and easy valorization of waste to valuable chemicals. PMID:26898679

  13. The effect of dietary fiber from wheat processing streams on the formation of carboxylic acids and microbiota in the hindgut of rats.

    Science.gov (United States)

    Haskå, Lina; Andersson, Roger; Nyman, Margareta

    2011-04-13

    Colonic fermentation of dietary fiber produces carboxylic acids and may stimulate the growth of beneficial bacteria. This study investigated how byproducts of wheat processing (distillers' grains and two fractions from the wet fractionation to starch and gluten, one of which was treated with xylanase) affect the composition of the cecal microbiota and the formation of carboxylic acids in rats. Differences were mostly found between diets based on supernatants and pellets, rather than between fiber sources. Cecal pools and levels of most carboxylic acids in portal blood were higher for rats fed the supernatant diets, while cecal pH and ratios of acetic to propionic acid in portal blood were lower. The diet based on supernatant from distillers' grains gave the highest level of bifidobacteria. Molecular weight and solubility are easier to modify with technological processes, which provides an opportunity to optimize these properties in the development of health products. PMID:21391670

  14. Crystal structure of ammonium (3,5-dichlorophenoxy)acetate hemihydrate

    OpenAIRE

    Graham Smith

    2015-01-01

    In the structure of the title hydrated salt, NH4+·C8H5Cl2O3−·0.5H2O, where the anion derives from (3,5-dichlorophenoxy)acetic acid, the ammonium cation is involved in extensive N—H...O hydrogen bonding with both carboxylate and ether O-atom acceptors giving sheet structures lying parallel to (100). The water molecule of solvation lies on a crystallographic twofold rotation axis and is involved in intra-sheet O—H...Ocarboxylate hydrogen-bonding interactions. In the anion, the oxoacetate side c...

  15. Conversion to eslicarbazepine acetate monotherapy

    OpenAIRE

    Sperling, Michael R.; French, Jacqueline; Jacobson, Mercedes P.; Pazdera, Ladislav; Gough, Mallory; Cheng, Hailong; Grinnell, Todd; Blum, David

    2016-01-01

    Objective: To assess the efficacy and safety of eslicarbazepine acetate (ESL) monotherapy. Methods: This post hoc pooled analysis of 2 randomized double-blind studies (093-045 and -046) included adults with partial-onset seizures medically uncontrolled by 1 or 2 antiepileptic drugs (AEDs). Following the baseline period (8 weeks), eligible patients were randomized 2:1 to receive ESL 1,600 mg or 1,200 mg once daily for 18 weeks; the primary endpoint was study exit by meeting predefined exit cri...

  16. A Novel NADPH-Dependent Aldehyde Reductase Gene from Saccharomyces cerevisiae NRRL Y-12632 Involved in the Detoxification of Aldehyde Inhibitors Derived from Lignocellulosic Biomass Conversion

    Science.gov (United States)

    Aldehyde inhibitors such as furfural, 5-hydroxymethylfurfural (HMF), anisaldehyde, benzaldehyde, cinnamaldehyde, and phenylaldehyde are commonly generated during lignocellulosic biomass conversion process for low-cost cellulosic ethanol production that interferes with subsequent microbial growth and...

  17. Oxidation of fatty aldehydes to fatty acids by Escherichia coli cells expressing the Vibrio harveyi fatty aldehyde dehydrogenase (FALDH).

    Science.gov (United States)

    Buchhaupt, Markus; Guder, Jan; Sporleder, Fenja; Paetzold, Melanie; Schrader, Jens

    2013-03-01

    Fatty acids represent an important renewable feedstock for the chemical industry. To enable biotechnological one carbon truncations of fatty acids, the enzymes α-dioxygenase and fatty aldehyde dehydrogenase (FALDH) have to be combined in a two-step process. We expressed an FALDH from V. harveyi in E. coli and characterized its substrate spectrum with a focus on the number and position of double bonds in the fatty aldehyde molecules. Synthesis of the expected fatty acid products was proven by analysis of whole cell biotransformation products. Coexpression of a H(2)O-forming NADPH oxidase (NOX) from Lactobacillus sanfranciscensis led to the implementation of a cofactor regeneration cycle in in vitro oxidation experiments. The presence of NOX in whole cell biotransformations improved reaction velocity but did not result in higher product yields. We could further demonstrate that at least part of the endogenous NAD(P)(+) regeneration capacity in the resting cells results from the respiratory chain. The whole cell catalyst with the high broad range FALDH activity described here is an important biotechnological module for lipid biotransformation processes, especially the shortening of fatty acids. PMID:23180547

  18. A specific affinity reagent to distinguish aldehyde dehydrogenases and oxidases. Enzymes catalyzing aldehyde oxidation in an adult moth

    International Nuclear Information System (INIS)

    Aldehyde dehydrogenase (ALDH) and oxidase (AO) enzymes from the tissue extracts of male and female tobacco budworm moth (Heliothis virescens) were identified after electrophoretic protein separation. AO activity was visualized using formazan- or horseradish peroxidase-mediated staining coupled to the AO-catalyzed oxidation of benzaldehyde. A set of six soluble AO enzymes with isoelectric points from pI 4.6 to 5.3 were detected primarily in the antennal extracts. Partially purified antennal AO enzymes also oxidized both (Z)-9-tetradecenal and (Z)-11-hexadecenal, the two major pheromone components of this moth. ALDH activity was detected using a tritium-labeled affinity reagent based on a known irreversible inhibitor of this enzyme. This labeled vinyl ketone, [3H](Z)-1,11-hexadecadien-3-one, was synthesized and used to covalently modify the soluble ALDH enzymes from tissue extracts. Molecular subunits of potential ALDH enzymes were visualized in the fluorescence autoradiograms of sodium dodecyl sulfate-polyacrylamide gel electrophoresis-separated proteins of the antenna, head, and leg tissues. Covalent modification of these protein subunits decreased specifically in the presence of excess pheromone aldehyde or benzaldehyde. Labeled vinyl ketones are thus novel tools for the identification of molecular subunits of ALDH enzymes

  19. Role and structural characterization of plant aldehyde dehydrogenases from family 2 and family 7

    Czech Academy of Sciences Publication Activity Database

    Končitíková, R.; Vigouroux, A.; Kopečná, M.; Andree, T.; Bartoš, Jan; Šebela, M.; Moréra, S.; Kopečný, D.

    2015-01-01

    Roč. 468, Part: 1 (2015), s. 109-123. ISSN 0264-6021 R&D Projects: GA ČR GA15-22322S; GA MŠk(CZ) LO1204 Institutional support: RVO:61389030 Keywords : aldehyde dehydrogenase 2 (ALDH2) * aldehyde dehydrogenase 7 (ALDH7) * benzaldehyde Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 4.396, year: 2014

  20. Draft Genome Sequence of Aldehyde-Degrading Strain Halomonas axialensis ACH-L-8

    OpenAIRE

    Ye, Jun; Ren, Chong; Shan, Xiexie; Zeng, Runying

    2016-01-01

    Halomonas axialensis ACH-L-8, a deep-sea strain isolated from the South China Sea, has the ability to degrade aldehydes. Here, we present an annotated draft genome sequence of this species, which could provide fundamental molecular information on the aldehydes-degrading mechanism.

  1. Draft Genome Sequence of Aldehyde-Degrading Strain Halomonas axialensis ACH-L-8.

    Science.gov (United States)

    Ye, Jun; Ren, Chong; Shan, Xiexie; Zeng, Runying

    2016-01-01

    Halomonas axialensisACH-L-8, a deep-sea strain isolated from the South China Sea, has the ability to degrade aldehydes. Here, we present an annotated draft genome sequence of this species, which could provide fundamental molecular information on the aldehydes-degrading mechanism. PMID:27081145

  2. Carboxylic Acid Esters as Substrates of Cholinesterases

    Science.gov (United States)

    Brestkin, A. P.; Rozengart, E. V.; Abduvakhabov, A. A.; Sadykov, A. A.

    1983-10-01

    Data on the kinetics of the hydrolysis of various carboxylic acid esters by two main types of cholinesterases — acetylcholinesterase from human erythrocytes and butyrylcholinesterase from horse blood serum — are surveyed. It is shown that the rate of enzyme hydrolysis depends significantly on the structure of the acyl part of the ester molecule, the nature of the ester heteroatom, the structure of the alcohol component, and particularly the structure of the onium group. Esters based on natural products are of special interest as specific substrates of these enzymes. The role of the productive and non-productive sorption of the substrates in enzyme catalysis is demonstrated. The bibliography includes 81 references.

  3. Synthesis of bio-based aldehyde from seaweed polysaccharide and its interaction with bovine serum albumin.

    Science.gov (United States)

    Kholiya, Faisal; Chaudhary, Jai Prakash; Vadodariya, Nilesh; Meena, Ramavatar

    2016-10-01

    Here, we demonstrate a successful synthesis of bio-based aldehyde namely dialdehyde-carboxymethylagarose (DCMA) using carboxymethyagarose (CMA). Further reaction parameters (i.e. reaction temperature, pH and periodate concentration) were optimized to achieve maximum aldehyde content and product yield. The synthesis of DCMA was confirmed by employing FTIR, (1)H NMR, XRD, SEM, AFM, TGA, DSC, EA and GPC techniques. To investigate the aldehyde functionality, DCMA was allowed to interact with BSA and obtained results were found to be comparable with that of synthetic aldehyde (Formaldehyde). Further interaction of DCMA with BSA was confirmed by using UV-vis, FTIR, fluorescent spectroscopy, CD and DLS analysis. Results of this study revealed that bio-based aldehyde behaves like formaldehyde. This study adds value to abundant marine biopolymers and opens the new research area for polymer researchers. PMID:27312639

  4. Flavour release of aldehydes and diacetyl in oil/water systems

    DEFF Research Database (Denmark)

    Haahr, Anne-Mette; Bredie, W. L. P.; Stahnke, Louise Heller; Jensen, B.; Refsgaard, Hanne

    2000-01-01

    The concentration- and time-dependent release of three C-6-aldehydes, six C-9-aldehydes and diacetyl was studied in model systems. The systems were water, rapeseed oil and oil-in-water emulsions. Dynamic headspace sampling was used to collect the volatile compounds. In the concentration......-dependent release experiment, the C-6-aldehydes were released in equal proportions from the aqueous and the emulsion systems, but in lower amounts from the pure oil. The amounts of C-9-aldehydes released decreased with increasing oil content. All aldehydes were released more rapidly from the aqueous system than...... from the pure oil. The release over time for diacetyl and (E,E)-2,4-hexadienal showed a linear relationship in all systems. The other compounds followed an exponential relationship between the time and the fraction released in the aqueous systems. It was demonstrated that the release of the volatile...

  5. Fatty aldehydes in cyanobacteria are a metabolically flexible precursor for a diversity of biofuel products.

    Directory of Open Access Journals (Sweden)

    Brett K Kaiser

    Full Text Available We describe how pathway engineering can be used to convert a single intermediate derived from lipid biosynthesis, fatty aldehydes, into a variety of biofuel precursors including alkanes, free fatty acids and wax esters. In cyanobacteria, long-chain acyl-ACPs can be reduced to fatty aldehydes, and then decarbonylated to alkanes. We discovered a cyanobacteria class-3 aldehyde-dehydrogenase, AldE, that was necessary and sufficient to instead oxidize fatty aldehyde precursors into fatty acids. Overexpression of enzymes in this pathway resulted in production of 50 to 100 fold more fatty acids than alkanes, and the fatty acids were secreted from the cell. Co-expression of acyl-ACP reductase, an alcohol-dehydrogenase and a wax-ester-synthase resulted in a third fate for fatty aldehydes: conversion to wax esters, which accumulated as intracellular lipid bodies. Conversion of acyl-ACP to fatty acids using endogenous cyanobacterial enzymes may allow biofuel production without transgenesis.

  6. Carboxylation and Decarboxylation of Aluminum Oxide Nanoparticles Using Bifunctional Carboxylic Acids and Octylamine

    Directory of Open Access Journals (Sweden)

    Shirin Alexander

    2016-01-01

    Full Text Available The carboxylation of alumina nanoparticles (NPs, with bifunctional carboxylic acids, provides molecular anchors that are used for building more complexed structures via either physisorption or chemisorption. Colloidal suspensions of the NPs may be prepared by covalently bonding a series of carboxylic acids with secondary functional groups (HO2C-R-X to the surface of the NPs: lysine (X = NH2, p-hydroxybenzoic acid (X = OH, fumaric acid (X = CO2H, and 4-formylbenzoic acid (X = C(OH. Subsequent reaction with octylamine at either 25°C or 70°C was investigated. Fourier transform IR-attenuated reflectance spectroscopy (FTIR-ATR, thermogravimetric analysis (TGA, and scanning electron microscopy (SEM along with energy dispersive X-ray (EDX analysis were used to characterize the bifunctionalized monolayers and/or multilayer corona surrounding the alumina NPs and investigate the reaction mechanism of octylamine with the functional groups (X of the NPs. Except for the fumaric functionalized NPs, addition of octylamine to the functionalized NPs leads to removal of excess carboxylic acid corona from the surface via an amide formation. The extent of the multilayer is dependent on the strength of the acid⋯acid interaction.

  7. Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

    Energy Technology Data Exchange (ETDEWEB)

    Saykally, Richard J; Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

    2008-01-08

    We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings.

  8. Oxidized cellulose esters: I. Preparation and characterization of oxidized cellulose acetates--a new class of biodegradable polymers.

    Science.gov (United States)

    Kumar, V; Yang, D

    2002-01-01

    Oxidized cellulose acetates (OCA), with a degree of substitution (DS) value ranging between 1.1 and 2.3 and a free carboxylic acid group content of 20% (w/w), have been prepared by reacting oxidized cellulose (OC, COOH content 20% w/w) with a mixture of acetic acid and acetic anhydride in the presence of sulfuric acid as a catalyst. The DS of OCA, in general, increased with increasing reaction temperature, reaction time, and concentration of acetic anhydride in the reaction mixture. The yield of OCA, in contrast, increased with increasing concentration of acetic anhydride and decreased with increasing reaction time and temperature. The intrinsic viscosity of OCA varied between 0.100 and 0.275, depending on the reaction conditions used during its preparation. In general, an increase in reaction temperature and the use of a prolonged reaction time decreased the intrinsic viscosity of OCA. No correlation was found between DS and intrinsic viscosity of OCA. The apparent pKa of OCA is 3.7-3.9. The new OCA polymers are practically insoluble in water and slowly dissolve in pH 7.4 phosphate buffer solution. They are, however, soluble in a range of organic solvents (e.g. ethyl acetate, acetone, acetone/water, chloroform/methylene chloride, dimethylsulfoxide, dimethylformamide, and/or chloroform/methanol). PMID:12102594

  9. Isobaric Vapor-Liquid Equilibrium of Binary Systems: p-Xylene + (Acetic Acid, Methyl Acetate and n-Propyl Acetate)and Methyl Acetate + n-Propyl Acetate in an Acetic Acid Dehydration Process

    Institute of Scientific and Technical Information of China (English)

    HUANG Xiuhui; ZHONG Weimin; PENG Changjun; QIAN Feng

    2013-01-01

    The vapor-liquid equilibrium data of four binary systems(acetic acid + p-xylene,methyl acetate + n-propyl acetate,n-propyl acetate + p-xylene and methyl acetate + p-xylene)are measured at 101.33 kPa with Ellis equilibrium still,and then both the NRTL and UNIQUAC models are used in combination with the HOC model for correlating and estimating the vapor-liquid equilibrium of these four binary systems.The estimated binary VLE results using correlated parameters agree well with the measured data except the methyl acetate + p-xylene system which easily causes bumping and liquid rushing out of the sampling tap due to their dramatically different boiling points.The correlation results by NRTL and UNIQUAC models have little difference on the average absolute deviations of temperature and composition of vapor phase,and the results by NRTL model are slightly better than those by UNIQUAC model except for the methyl acetate + n-propyl acetate system,for which the latter gives more accurate correlations.

  10. Monolayer structures of alkyl aldehydes: Odd-membered homologues

    Energy Technology Data Exchange (ETDEWEB)

    Phillips, T.K. [BP Institute, Department of Chemistry, University of Cambridge, Cambridge (United Kingdom); Clarke, S.M., E-mail: stuart@bpi.cam.ac.u [BP Institute, Department of Chemistry, University of Cambridge, Cambridge (United Kingdom); Bhinde, T. [BP Institute, Department of Chemistry, University of Cambridge, Cambridge (United Kingdom); Castro, M.A.; Millan, C. [Instituto Ciencia de los Materiales de Sevilla, Departamento de Quimica Inorganica (CSIC-Universidad de Sevilla) (Spain); Medina, S. [Centro de Investigacion, Tecnologia e Innovacion de la Universidad de Sevilla (CITIUS), Sevilla (Spain)

    2011-03-01

    Crystalline monolayers of three aldehydes with an odd number of carbon atoms in the alkyl chain (C{sub 7}, C{sub 9} and C{sub 11}) at low coverages are observed by a combination of X-ray and neutron diffraction. Analysis of the diffraction data is discussed and possible monolayer crystal structures are proposed; although unique structures could not be ascertained for all molecules. We conclude that the structures are flat on the surface, with the molecules lying in the plane of the layer. The C{sub 11} homologue is determined to have a plane group of either p2, pgb or pgg, and for the C{sub 7} homologue the p2 plane group is preferred.

  11. Reduction of Aldehydes and Ketones with Potassium Borohydride as Reductant

    Institute of Scientific and Technical Information of China (English)

    罗慧谋; 李毅群

    2005-01-01

    A series of aldehydes and ketones were reduced by potassium borohydride in an ionic liquid/water ([bmim]PF6/H2O) biphasic system to afford corresponding alcohol with high purity in excellent yields. The ionic liquid/water biphasic system could promote the chemoselectivity and the substituents such as nitro group and chlorine remained intact. Aromatic ketones were not as active as aromatic aldhydes and cyclic ketones owing to their higher steric hindrance. The ionic liquid could be recycled and reused. This protocol has notable advantages of no need of phase transfer catalyst and organic solvents, mild conditions, simple operation, short reaction time, ease work-up, high yields and recycling of the ionic liquid.

  12. Understanding Palladium Acetate from a User Perspective.

    Science.gov (United States)

    Carole, William A; Colacot, Thomas J

    2016-06-01

    The behavior of palladium acetate is reviewed with respect to its synthesis, characterization, structure (in both solution and solid state), and activation pathways. In addition, comparisons of catalytic activities between pure palladium acetate and two common byproducts, Pd3 (OAc)5 (NO2 ) and polymeric [Pd(OAc)2 ]n , typically present in commercially available material are reviewed. Hence, this minireview serves as a concise guide for the users of palladium acetate from both academia and industry. PMID:27125630

  13. Pharmacological activities of cilantro's aliphatic aldehydes against Leishmania donovani.

    Science.gov (United States)

    Donega, Mateus A; Mello, Simone C; Moraes, Rita M; Jain, Surendra K; Tekwani, Babu L; Cantrell, Charles L

    2014-12-01

    Leishmaniasis is a chronic infectious disease caused by different Leishmania species. Global occurrences of this disease are primarily limited to tropical and subtropical regions. Treatments are available; however, patients complain of side effects. Different species of plants have been screened as a potential source of new drugs against leishmaniasis. In this study, we investigated the antileishmanial activity of cilantro (Coriandrum sativum) essential oil and its main components: (E)-2-undecenal, (E)-2-decenal, (E)-2-dodecenal, decanal, dodecanal, and tetradecanal. The essential oil of C. sativum leaves inhibits growth of Leishmani donovani promastigotes in culture with an IC50 of 26.58 ± 6.11 µg/mL. The aliphatic aldehydes (E)-2-decenal (7.85 ± 0.28 µg/mL), (E)-2-undecenal (2.81 ± 0.21 µg/mL), and (E)-2-dodecenal (4.35 ± 0.15 µg/mL), all isolated from C. sativum essential oil, are effective inhibitors of in vitro cultures of L. donovani promastigotes. Aldehydes (E)-2-decenal, (E)-2-undecenal, and (E)-2-dodecenal were also evaluated against axenic amastigotes and IC50 values were determined to be 2.47 ± 0.25 µg/mL, 1.25 ± 0.11 µg/mL, and 4.78 ± 1.12 µg/mL, respectively. (E)-2-Undecenal and (E)-2-dodecenal demonstrated IC50 values of 5.65 ± 0.19 µg/mL and 9.60 ± 0.89 µg/mL, respectively, against macrophage amastigotes. These cilantro compounds showed no cytotoxicity against THP-1 macrophages. PMID:25340465

  14. Targeting aldehyde dehydrogenase: a potential approach for cell labeling

    Energy Technology Data Exchange (ETDEWEB)

    Vaidyanathan, Ganesan [Department of Radiology, Duke University Medical Center, Box 3808, Durham, NC 27710 (United States)], E-mail: ganesan.v@duke.edu; Song, Haijing; Affleck, Donna; McDougald, Darryl L. [Department of Radiology, Duke University Medical Center, Box 3808, Durham, NC 27710 (United States); Storms, Robert W. [Division of Cellular Therapy, Department of Medicine, Duke University Medical Center, Durham, NC 27710 (United States); Zalutsky, Michael R.; Chin, Bennett B. [Department of Radiology, Duke University Medical Center, Box 3808, Durham, NC 27710 (United States)

    2009-11-15

    Introduction: To advance the science and clinical application of stem cell therapy, the availability of a highly sensitive, quantitative and translational method for tracking stem cells would be invaluable. Because hematopoetic stem cells express high levels of the cytosolic enzyme aldehyde dehydrogenase-1A1 (ALDH1), we sought to develop an agent that is specific to ALDH1 and thus to cells expressing the enzyme. Such an agent might be also helpful in identifying tumors that are resistant to cyclophosphomide chemotherapy because ALDH1 is known to be responsible for this resistance. Methods: We developed schemes for the synthesis of two radioiodinated aldehdyes - N-formylmethyl-5-[*I]iodopyridine-3-carboxamide ([*I]FMIC) and 4-diethylamino-3-[*I]iodobenzaldehyde ([*I]DEIBA)-at no-carrier-added levels from their respective tin precursors. These agents were evaluated using pure ALDH1 and tumor cells that expressed the enzyme. Results: The average radiochemical yields for the synthesis of [{sup 125}I]FMIC and [{sup 125}I]DEIBA were 70{+-}5% and 47{+-}14%, respectively. ALDH1 converted both compounds to respective acids suggesting their suitability as ALDH1 imaging agents. Although ability of ALDH1 within the cells to oxidize one of these substrates was shown, specific uptake in ALDH-expressing tumor cells could not be demonstrated. Conclusion: To pursue this approach for ALDH1 imaging, radiolabeled aldehydes need to be designed such that, in addition to being good substrates for ALDH1, the cognate products should be sufficiently polar so as to be retained within the cells.

  15. Targeting aldehyde dehydrogenase: a potential approach for cell labeling

    International Nuclear Information System (INIS)

    Introduction: To advance the science and clinical application of stem cell therapy, the availability of a highly sensitive, quantitative and translational method for tracking stem cells would be invaluable. Because hematopoetic stem cells express high levels of the cytosolic enzyme aldehyde dehydrogenase-1A1 (ALDH1), we sought to develop an agent that is specific to ALDH1 and thus to cells expressing the enzyme. Such an agent might be also helpful in identifying tumors that are resistant to cyclophosphomide chemotherapy because ALDH1 is known to be responsible for this resistance. Methods: We developed schemes for the synthesis of two radioiodinated aldehdyes - N-formylmethyl-5-[*I]iodopyridine-3-carboxamide ([*I]FMIC) and 4-diethylamino-3-[*I]iodobenzaldehyde ([*I]DEIBA)-at no-carrier-added levels from their respective tin precursors. These agents were evaluated using pure ALDH1 and tumor cells that expressed the enzyme. Results: The average radiochemical yields for the synthesis of [125I]FMIC and [125I]DEIBA were 70±5% and 47±14%, respectively. ALDH1 converted both compounds to respective acids suggesting their suitability as ALDH1 imaging agents. Although ability of ALDH1 within the cells to oxidize one of these substrates was shown, specific uptake in ALDH-expressing tumor cells could not be demonstrated. Conclusion: To pursue this approach for ALDH1 imaging, radiolabeled aldehydes need to be designed such that, in addition to being good substrates for ALDH1, the cognate products should be sufficiently polar so as to be retained within the cells.

  16. Quantification of Carnosine-Aldehyde Adducts in Human Urine.

    Science.gov (United States)

    da Silva Bispo, Vanderson; Di Mascio, Paolo; Medeiros, Marisa

    2014-10-01

    Lipid peroxidation generates several reactive carbonyl species, including 4-hydroxy-2-nonenal (HNE), acrolein (ACR), 4-hydroxy-2-hexenal (HHE) and malondialdehyde. One major pathwayof aldehydes detoxification is through conjugation with glutathione catalyzed by glutathione-S-transferases or, alternatively, by conjugation with endogenous histidine containing dipeptides, such as carnosine (CAR). In this study, on-line reverse-phase high-performance liquid chromatography (HPLC) separation with tandem mass spectrometry detection was utilized for the accurate quantification of CAR- ACR, CAR-HHE and CAR-HNE adducts in human urinary samples from non-smokers young adults. Standard adducts were prepared and isolated by HPLC. The results showed the presence of a new product from the reaction of CAR with ACR. This new adduct was completely characterized by HPLC/MS-MSn, 1H RMN, COSY and HSQC. The new HPLC/MS/MS methodology employing stable isotope-labeled internal standards (CAR-HHEd5 and CAR-HNEd11) was developed for adducts quantification. This methodology permits quantification of 10pmol CAR-HHE and 1pmol of CAR-ACR and CAR-HNE. Accurate determinations in human urine sample were performed and showed 4.65±1.71 to CAR-ACR, 5.13±1.76 to CAR-HHE and 5.99±3.19nmol/mg creatinine to CAR-HNE. Our results indicate that carnosine pathways can be an important detoxification route of a, ß -unsaturated aldehydes. Moreover, carnosine adducts may be useful as redox stress indicator. PMID:26461323

  17. Formic and acetic acid: Valence threshold photoelectron and photoionisation total ion yield studies

    International Nuclear Information System (INIS)

    Highlights: ► High-resolution threshold photoelectron spectrum of formic acid. ► High-resolution total photo-ion yield spectrum of formic acid. ► High-resolution threshold photoelectron spectrum of acetic acid. ► High-resolution total photo-ion yield spectrum of acetic acid. -- Abstract: The carboxylic acids (formic and acetic) have been studied using threshold photoelectron (TPE) and total photoion yield (TPIY) spectroscopies; simultaneously obtained spectra of formic acid (HCOOH) were recorded over the entire valence ionisation region from 11–21 eV at a resolution of ∼12 meV. Higher resolution spectra (∼6 meV) were also obtained in the energy region of the lowest two cationic states. Analysis of the TPE spectrum in this energy range agreed very favorably with the best available conventional photoelectron (PE) spectrum of formic acid. Autoionising Rydberg structure was observed in the TPIY spectrum of formic acid and is attributed primarily to the presence of the npa′ ← 8a′ Rydberg series converging on to the 32A′ ionic state of formic acid. Preliminary results, at a resolution of ∼8 meV, were obtained for acetic acid (CH3COOH) over the onset of the ionisation energy region. The TPE spectrum was found to be very similar to the best published photoelectron spectrum, but no Rydberg structure was observed in the TPIY spectrum.

  18. Synthesis and Structural Characterization of 1- and 2-Substituted Indazoles: Ester and Carboxylic Acid Derivatives

    Directory of Open Access Journals (Sweden)

    Isabel Bento

    2006-11-01

    Full Text Available A series of indazoles substituted at the N-1 and N-2 positions with ester-containing side chains -(CH2nCO2R of different lengths (n = 0-6, 9, 10 are described.Nucleophilic substitution reactions on halo esters (X(CH2nCO2R by 1H-indazole inalkaline solution lead to mixtures of N-1 and N-2 isomers, in which the N-1 isomerpredominates. Basic hydrolysis of the ester derivatives allowed the synthesis of thecorresponding indazole carboxylic acids. All compounds were fully characterised bymultinuclear NMR and IR spectroscopies, MS spectrometry and elemental analysis; theNMR spectroscopic data were used for structural assignment of the N-1 and N-2 isomers.The molecular structure of indazol-2-yl-acetic acid (5b was determined by X-raydiffraction, which shows a supramolecular architecture involving O2-H...N1intermolecular hydrogen bonds.

  19. Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes

    Science.gov (United States)

    Krause, Thilo; Baader, Sabrina; Erb, Benjamin; Gooßen, Lukas J.

    2016-01-01

    Amide bond-forming reactions are of tremendous significance in synthetic chemistry. Methodological research has, in the past, focused on efficiency and selectivity, and these have reached impressive levels. However, the unacceptable amounts of waste produced have led the ACS GCI Roundtable to label ‘amide bond formation avoiding poor atom economy' as the most pressing target for sustainable synthetic method development. In response to this acute demand, we herein disclose an efficient one-pot amide coupling protocol that is based on simple alkynes as coupling reagents: in the presence of a dichloro[(2,6,10-dodecatriene)-1,12-diyl]ruthenium catalyst, carboxylate salts of primary or secondary amines react with acetylene or ethoxyacetylene to vinyl ester intermediates, which undergo aminolysis to give the corresponding amides along only with volatile acetaldehyde or ethyl acetate, respectively. The new amide synthesis is broadly applicable to the synthesis of structurally diverse amides, including dipeptides. PMID:27282773

  20. Atom-economic catalytic amide synthesis from amines and carboxylic acids activated in situ with acetylenes.

    Science.gov (United States)

    Krause, Thilo; Baader, Sabrina; Erb, Benjamin; Gooßen, Lukas J

    2016-01-01

    Amide bond-forming reactions are of tremendous significance in synthetic chemistry. Methodological research has, in the past, focused on efficiency and selectivity, and these have reached impressive levels. However, the unacceptable amounts of waste produced have led the ACS GCI Roundtable to label 'amide bond formation avoiding poor atom economy' as the most pressing target for sustainable synthetic method development. In response to this acute demand, we herein disclose an efficient one-pot amide coupling protocol that is based on simple alkynes as coupling reagents: in the presence of a dichloro[(2,6,10-dodecatriene)-1,12-diyl]ruthenium catalyst, carboxylate salts of primary or secondary amines react with acetylene or ethoxyacetylene to vinyl ester intermediates, which undergo aminolysis to give the corresponding amides along only with volatile acetaldehyde or ethyl acetate, respectively. The new amide synthesis is broadly applicable to the synthesis of structurally diverse amides, including dipeptides. PMID:27282773

  1. [Effects of panthenol and carnitine on aldehyde metabolic enzymes in rats with tetrachloromethane-induced liver injury].

    Science.gov (United States)

    Satanovskaia, V I; Pron'ko, P S; Gaĭshmanova, A V; Miskevich, D A

    2009-01-01

    Tetrachloromethane (2 g/kg, intragastric) produced a decrease in the activity of NAD- and NADH- dependent aldehyde dehydrogenases with high Km for aldehydes in rat liver. Panthenol and L-carnitine administered separately normalized the activity of aldehyde dehydrogenases, while a combination of the drugs did not produce any significant effect. PMID:19441727

  2. Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: Thermal and mechanical properties

    OpenAIRE

    H. F. Xie; Wang, Y. T.; Wang, C. S.; H. Y. Yin; Wang, L.L.; R. S. Cheng

    2012-01-01

    Carboxyl-modified multi-walled carbon nanotubes (MWCNT–COOHs) as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA) toughened with carboxyl-terminated butadiene-acrylonitrile (CTBN). The carboxyl functional carbon nanotubes were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. Furthermore, cure kinetics, glass transition temperature (Tg), mechanical properties, thermal stability and morphology of DGEBA/CTBN/MWCNT–COOH...

  3. Solubilities of carbon dioxide in 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate and 3-methoxybutyl acetate

    International Nuclear Information System (INIS)

    Highlights: • Measured solubility data of CO2 in 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate and 3-methoxybutyl acetate. • Calculated Henry’s constant and thermodynamic properties of selected systems. • Concluded that selected absorbents have potential research value for CO2 capture. - Abstract: The solubilities of CO2 in 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, and 3-methoxybutyl acetate were measured by isothermal synthesis method under pressures up to 1.2 MPa and at temperatures ranging from (293.15 to 333.15) K. Henry’s constant was calculated based on experimental data regression. The solubilities of CO2 were found to increase with decreased temperature and increased the methyl group to the molecular structure of the absorbent. Henry’s constant and volumetric solubility of selected absorbents at T = 298.15 K were compared with those of commercial absorbents and common solvents. 3-Methoxybutyl acetate showed the best performance by mole fraction, and 2-methoxyethyl acetate behaved the best by volumetric fraction. Based on Henry’s constant, thermodynamic properties such as Gibbs free energy of solution, enthalpy of solution, and absorption entropy of solution were determined. These properties are very essential for designing an absorption process

  4. Stability study of ZnO nanoparticles in aqueous solutions of carboxylate anions

    Energy Technology Data Exchange (ETDEWEB)

    Godymchuk, Anna, E-mail: godymchuk@tpu.ru; Karepina, Elizaveta; Yunda, Elena; Lyamina, Galina [National Research Tomsk Polytechnic University (Russian Federation); Kosova, Natalia [National Research Tomsk State University (Russian Federation); Kuznetsov, Denis [National University of Science and Technology “MISiS” (Russian Federation)

    2015-03-15

    The paper is devoted to the use of carboxylic acids and salts for the elaboration of stable suspensions of ZnO engineered nanoparticles (40 and 200 nm) in physiological media at pH 6–8. It was shown that the aggregation degree of ZnO-200 particles increases with the growth of carboxylic anion activity, e.g., at pH 7 in the row «Acetate{sup −}–Citrate{sup 3−}–Oxalate{sup 2−}» the average size of ZnO-200 particles in suspensions amounts to «169–523–770» nm, zeta potential–«35.9–−19.9–+5.42 mV», respectively. The aggregation degree of ZnO-40 particles increases in the row «Citrate{sup 3−}–Acetate{sup −}–Oxalate{sup 2−}», at pH 7, the average size of ZnO-40 particles in suspension amounts to «50–121–430» nm, zeta potential–«−28.3–−14.5–+2.3» mV, respectively. pH-impact was found to be size-dependent: there was a significantly less effect of pH on adsorption, dispersion, and electrokinetic properties of ZnO-40 particles when compared to ZnO-200 particles. The main reason for the difference between micro- and nanosized particles behavior is a change of the ratio of acidic, basic, and neutral Bronsted centers for particles of nanosized scale.

  5. Inhibition of Vibrio harveyi bioluminescence by cerulenin: In vivo evidence for covalent modification of the reductase enzyme involved in aldehyde synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Byers, D.M. (Dalhousie Univ., Halifax (Nova Scotia)); Meighen, E.A. (McGill Univ., Montreal, Quebec (Canada))

    1989-07-01

    Bacterial bioluminescence is very sensitive to cerulenin, a fungal antibiotic which is known to inhibit fatty acid synthesis. When Vibrio harveyi cells pretreated with cerulenin were incubated with ({sup 3}H)myristic acid in vivo, acylation of the 57-kilodalton reductase subunit of the luminescence-specific fatty acid reductase complex was specifically inhibited. Light emission of wild-type V. harveyi was 20-fold less sensitive to cerulenin at low concentrations (10{mu}g/ml) than that of the dark mutant strain M17, which requires exogenous myristic acid for luminescence because of a defective transferase subunit. The sensitivity of myristic acid-stimulated luminescence in the mutant strain M17 exceeded that of phospholipid synthesis from ({sup 14}C)acetate, whereas uptake and incorporation of exogenous ({sup 14}C)myristic acid into phospholipids was increased by cerulenin. The reductase subunit could be labeled by incubating M17 cells with ({sup 3}H)tetrahydrocerulenin; this labeling was prevented by preincubation with either unlabeled cerulenin or myristic acid. Labeling of the reductase subunit with ({sup 3}H)tetrahydrocerulenin was also noted in an aldehyde-stimulated mutant (A16) but not in wild-type cells or in another aldehyde-stimulated mutant (M42) in which ({sup 3}H)myristoyl turnover at the reductase subunit was found to be defective. These results indicate that (i) cerulenin specifically and covalently inhibits the reductase component of aldehyde synthesis, (ii) this enzyme is partially protected from cerulenin inhibition in the wild-type strain in vivo, and (iii) two dark mutants which exhibit similar luminescence phenotypes (mutants A16 and M42) are blocked at different stages of fatty acid reduction.

  6. Inhibition of Vibrio harveyi bioluminescence by cerulenin: In vivo evidence for covalent modification of the reductase enzyme involved in aldehyde synthesis

    International Nuclear Information System (INIS)

    Bacterial bioluminescence is very sensitive to cerulenin, a fungal antibiotic which is known to inhibit fatty acid synthesis. When Vibrio harveyi cells pretreated with cerulenin were incubated with [3H]myristic acid in vivo, acylation of the 57-kilodalton reductase subunit of the luminescence-specific fatty acid reductase complex was specifically inhibited. Light emission of wild-type V. harveyi was 20-fold less sensitive to cerulenin at low concentrations (10μg/ml) than that of the dark mutant strain M17, which requires exogenous myristic acid for luminescence because of a defective transferase subunit. The sensitivity of myristic acid-stimulated luminescence in the mutant strain M17 exceeded that of phospholipid synthesis from [14C]acetate, whereas uptake and incorporation of exogenous [14C]myristic acid into phospholipids was increased by cerulenin. The reductase subunit could be labeled by incubating M17 cells with [3H]tetrahydrocerulenin; this labeling was prevented by preincubation with either unlabeled cerulenin or myristic acid. Labeling of the reductase subunit with [3H]tetrahydrocerulenin was also noted in an aldehyde-stimulated mutant (A16) but not in wild-type cells or in another aldehyde-stimulated mutant (M42) in which [3H]myristoyl turnover at the reductase subunit was found to be defective. These results indicate that (i) cerulenin specifically and covalently inhibits the reductase component of aldehyde synthesis, (ii) this enzyme is partially protected from cerulenin inhibition in the wild-type strain in vivo, and (iii) two dark mutants which exhibit similar luminescence phenotypes (mutants A16 and M42) are blocked at different stages of fatty acid reduction

  7. Contribution to the study of 14C-acetate as the precursor of aminoacids in detached leaves of coffee (Coffea arabica cv. Mundo Novo)

    International Nuclear Information System (INIS)

    Labelled acetates with 14C were used as the forerunner of aminoacids in leaves of coffee (Coffea arabica cv Mundo Novo). Leaves with the labelled acetates were incubated and released CO2 was retained in paper discs with hiamine for further radioactivity detection. Separated proteins furnished 13 amino-acids through acid hidrolysis, all of them were identified by bidimensional filter paper chromatography. Through the obtained results it is possible to conclude that acetates are metabolized by the leafs and are related to the processes of leaf synthesis. It was possible to show that an utilization of acetate for energetical production via Krebs cycle was donne. The obtained conclusions show too that methylic carbon was more incorporated than carboxylic carbon

  8. In Vitro Reactivity of Carboxylic Acid-CoA Thioesters with Glutathione

    DEFF Research Database (Denmark)

    Sidenius, Ulrik; Skonberg, Christian; Olsen, Jørgen;

    2004-01-01

    was to investigate whether a correlation could be found between the structure of acyl-CoA thioesters and their reactivities toward the tripeptide, glutathione (ç- Glu-Cys-Gly).  The  acyl-CoA  thioesters  of  eight  carboxylic  acids  (ibuprofen,  clofibric  acid, indomethacin,  fenbufen,  tolmetin,  salicylic  acid......The chemical reactivity of acyl-CoA thioesters toward nucleophiles has been demonstrated in several recent studies. Thus, intracellularly formed acyl-CoAs of xenobiotic carboxylic acids may react covalently with endogenous proteins and potentially lead to adverse effects. The purpose of this study......,  2-phenoxypropionic  acid,  and  (4-chloro-2-methyl-phenoxy)acetic  acid  (MCPA))  were  synthesized,  and  each  acyl-CoA  (0.5  mM)  was incubated with glutathione (5.0 mM) in 0.1 M potassium phosphate (pH 7.4, 37 °C). All of the acyl-CoAs reacted with glutathione to form the respective acyl...

  9. α,β-Unsaturated aldehyde of hyaluronan--Synthesis, analysis and applications.

    Science.gov (United States)

    Buffa, Radovan; Šedová, Petra; Basarabová, Ivana; Moravcová, Martina; Wolfová, Lucie; Bobula, Tomáš; Velebný, Vladimír

    2015-12-10

    Hyaluronic acid (HA) modified with an aldehyde group (HA-CHO or HA-aldehyde) has been extensively used for various biomedical applications. The main advantage of the aldehyde moieties is the ability to react with a wide range of amino compounds under physiological conditions. Reactions of aldehydes with primary amines in water are reversible and equilibrium is thoroughly shifted towards starting aldehyde and amine. This work presents an unique modification of HA: α,β-unsaturated aldehyde of HA (4,5-anhydro-6(GlcNAc)-oxo HA or ΔHA-CHO), which allows the primary amines to be attached to HA more effectively in comparison to the saturated HA-CHO. Higher hydrolytic stability is caused by the conjugation of imine with an adjacent --C=C-- double bond. Two strategies for the preparation of unsaturated HA-aldehyde were developed and chemical structures were studied in details. Cross-linked materials prepared from this precursor are biocompatible and suitable for applications in drug delivery and regenerative medicine. PMID:26428127

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

    International Nuclear Information System (INIS)

    The role of fatty aldehyde dehydrogenases (FALDHs) in hexadecane and hexadecanol metabolism was studied in Acinetobacter sp. strain HO1-N. Two distinct FALDHs were demonstrated in Acinetobacter sp. strain HO1-N: (i) a membrane-bound, NADP-dependent FALDH activity induced 5-, 15-, and 9 fold by growth on hexadecanol, dodecyl aldehyde, and hexadecane, respectively, and (ii) a constitutive, NAD-dependent, membrane-localized FALDH. Dodecyl aldehyde-negative mutants were isolated and grouped into two phenotypic classes based on growth: class 1 mutants were hexadecane and hexadecanol negative and class 2 mutants were hexadecane and hexadecanol positive. Specific activity of NADP-dependent FALDH in Ald21 (class 1 mutant) was 85% lower than that of wild-type FALDH, while the specific activity of Ald24 (class 2 mutant) was 55% greater than that of wild-type FALDH. Ald21R, a dodecyl aldehyde-positive revertant able to grow on hexadecane, hexadecanol, and dodecyl aldehyde, exhibited a 100% increase in the specific activity of the NADP-dependent FALDH. This study provides genetic and physiological evidence for the role of fatty aldehyde as an essential metabolic intermediate and NADP-dependent FALDH as a key enzyme in the dissimilation of hexadecane, hexadecanol, and dodecyl aldehyde in Acinetobacter sp. strain HO1-N

  11. Human brain aldehyde reductases: relationship to succinic semialdehyde reductase and aldose reductase.

    Science.gov (United States)

    Hoffman, P L; Wermuth, B; von Wartburg, J P

    1980-08-01

    Human brain contains multiple forms of aldehyde-reducing enzymes. One major form (AR3), as previously shown, has properties that indicate its identity with NADPH-dependent aldehyde reductase isolated from brain and other organs of various species; i.e., low molecular weight, use of NADPH as the preferred cofactor, and sensitivity to inhibition by barbiturates. A second form of aldehyde reductase ("SSA reductase") specifically reduces succinic semialdehyde (SSA) to produce gamma-hydroxybutyrate. This enzyme form has a higher molecular weight than AR3, and uses NADH as well as NADPH as cofactor. SSA reductase was not inhibited by pyrazole, oxalate, or barbiturates, and the only effective inhibitor found was the flavonoid quercetine. Although AR3 can also reduce SSA, the relative specificity of SSA reductase may enhance its in vivo role. A third form of human brain aldehyde reductase, AR2, appears to be comparable to aldose reductases characterized in several species, on the basis of its activity pattern with various sugar aldehydes and its response to characteristic inhibitors and activators, as well as kinetic parameters. This enzyme is also the most active in reducing the aldehyde derivatives of biogenic amines. These studies suggest that the various forms of human brain aldehyde reductases may have specific physiological functions. PMID:6778961

  12. Optimization of coproduction of ethyl acetate and n-butyl acetate by reactive distillation☆

    Institute of Scientific and Technical Information of China (English)

    Hui Tian; Suying Zhao; Huidong Zheng; Zhixian Huang

    2015-01-01

    Based on a previous investigation, a simulation model was used for optimization of coproduction of ethyl acetate and n-butyl acetate by reactive distil ation. An experimental setup was established to verify the simulated results. The effects of various operating variables, such as ethanol feed location, acetic acid feed location, feed stage of reaction mixture of acetic acid and n-butanol, reflux ratio of ethyl acetate reactive distillation column, and distil-late to feed ratio of n-butyl acetate column, on the ethanol/n-butanol conversions, ethyl acetate/n-butyl acetate purity, and energy consumption were investigated. The optimal results in the simulation study are as follows:ethanol feed location, 15th stage;acetic acid feed location, eighth stage;feed location of reaction mixture of acetic acid and n-butanol, eighth stage;reflux ratio of ethyl acetate reactive distillation column, 2.0;and distillate to feed ratio of n-butyl acetate, 0.6.

  13. 2-(Carboxymethylsulfanylpyridine-3-carboxylic acid monohydrate

    Directory of Open Access Journals (Sweden)

    Xiao-Juan Wang

    2010-06-01

    Full Text Available The title compound, C8H7NO4S·H2O, was obtained by reaction of 2-mercaptopyridine-3-carboxylic acid with chloroacetic acid. In the molecular structure, the dihedral angle between the two least-squares planes defined by the pyridine ring and the carboxy group is 8.32 (9°. The carboxymethylsulfanyl group makes a torsion angle of 82.64 (12° with the pyridine ring. An intramolecular O—H...N hydrogen bond between the acidic function of the carboxymethylsulfanyl group and the pyridine N atom stabilizes the conformation, whereas intermolecular O—H...O hydrogen bonding with the uncoordinated water molecules is responsible for packing of the structure, leading to chains propagating in [001].

  14. Direct Oxidation of Ethene to Acetic Acid

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Direct oxidation of ethene to acetic acid over Pd-SiW12/SiO2 catalysts prepared by several methods was studied. A better method for reducing palladium composition of the catalysts was found. Acetic acid was obtained with selectivity of 82.7% and once-through space time yield (STY) of 257.4 g/h×L.

  15. Carbon-isotopic analysis of dissolved acetate

    International Nuclear Information System (INIS)

    Heating of dried, acetate-containing solids together with oxalic acid dihydrate conveniently releases acetic acid for purification by gas chromatography. For determination of the carbon-isotopic composition of total acetate, the acetate-containing zone of the chromatographic effluent can be routed directly to a combustion furnace coupled to a vacuum system allowing recovery, purification, and packaging of CO2 for mass-spectrometric analysis. For analysis of methyl carbon, acetic acid can be cryogenically trapped from the chromatographic effluent, then transferred to a tube containing excess NaOH. The tube is evacuated, sealed, and heated to 500 degree C to produce methane by pyrolysis of sodium acetate. Subsequent combustion of the methane allows determination of the 13C content at the methyl position in the parent acetate. With typical blanks, the standard deviation of single analyses is less than 0.4 per-thousand for acetate samples larger than 5 μmol. A full treatment of uncertainties is outlined

  16. 21 CFR 173.228 - Ethyl acetate.

    Science.gov (United States)

    2010-04-01

    ... the specifications of the Food Chemicals Codex, 1 (Ethyl Acetate; p. 372, 3d Ed., 1981), which are... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethyl acetate. 173.228 Section 173.228 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR...

  17. Boron-containing amino carboxylic acid compounds and uses thereof

    International Nuclear Information System (INIS)

    Novel compounds which are useful for boron neutron capture therapy (BNCT) are disclosed. The compounds comprise a stable boron-containing group and an aminocycloalkane carboxylic acid group or a boronated acyclic hydrocarbon-linked amino carboxylic acid. Methods for synthesis of the compounds and for use of the compounds in BNCT are disclosed

  18. Lysine carboxylation: unveiling a spontaneous post-translational modification

    International Nuclear Information System (INIS)

    A computational method for the prediction of lysine carboxylation (KCX) in protein structures is described. The method accurately identifies misreported KCXs and predicts previously unknown KCX sites. The carboxylation of lysine residues is a post-translational modification (PTM) that plays a critical role in the catalytic mechanisms of several important enzymes. It occurs spontaneously under certain physicochemical conditions, but is difficult to detect experimentally. Its full impact is unknown. In this work, the signature microenvironment of lysine-carboxylation sites has been characterized. In addition, a computational method called Predictor of Lysine Carboxylation (PreLysCar) for the detection of lysine carboxylation in proteins with available three-dimensional structures has been developed. The likely prevalence of lysine carboxylation in the proteome was assessed through large-scale computations. The results suggest that about 1.3% of large proteins may contain a carboxylated lysine residue. This unexpected prevalence of lysine carboxylation implies an enrichment of reactions in which it may play functional roles. The results also suggest that by switching enzymes on and off under appropriate physicochemical conditions spontaneous PTMs may serve as an important and widely used efficient biological machinery for regulation

  19. Antimony(v) cations for the selective catalytic transformation of aldehydes into symmetric ethers, α,β-unsaturated aldehydes, and 1,3,5-trioxanes.

    Science.gov (United States)

    Arias Ugarte, Renzo; Devarajan, Deepa; Mushinski, Ryan M; Hudnall, Todd W

    2016-07-01

    1-Diphenylphosphinonaphthyl-8-triphenylstibonium triflate ([][OTf]) was prepared in excellent yield by treating 1-lithio-8-diphenylphosphinonaphthalene with dibromotriphenylstiborane followed by halide abstraction with AgOTf. This antimony(v) cation was found to be stable toward oxygen and water, and exhibited exceptional Lewis acidity. The Lewis acidity of [][OTf] was exploited in the catalytic reductive coupling of a variety of aldehydes into symmetric ethers of type in good to excellent yields under mild conditions using Et3SiH as the reductant. Additionally, [][OTf] was found to selectively catalyze the Aldol condensation reaction to afford α-β unsaturated aldehydes () when aldehydes with 2 α-hydrogen atoms were used. Finally, [][OTf] catalyzed the cyclotrimerization of aliphatic and aromatic aldehydes to afford the industrially-useful 1,3,5 trioxanes () in good yields, and with great selectivity. This phosphine-stibonium motif represents one of the first catalytic systems of its kind that is able to catalyze these reactions with aldehydes in a controlled, efficient manner. The mechanism of these processes has been explored both experimentally and theoretically. In all cases the Lewis acidic nature of the antimony(v) cation was found to promote these reactions. PMID:27326797

  20. The carbonyl oxide-aldehyde complex: a new intermediate of the ozonolysis reaction

    Science.gov (United States)

    Cremer, Dieter; Kraka, Elfi; McKee, M. L.; Radharkrishnan, T. P.

    1991-12-01

    MP4(SDQ)/6-31G (d,p) calculations suggest that the ozonolysis of alkenes in solution phase does not proceed via carbonyl oxide, but via a dipole complex between aldehyde and carbonyl oxide, which is 9 kcal/mol more stable than the separated molecules. The dipole complex is probably formed in the solvent cage upon decomposition of primary ozonide to aldehyde and carbonyl oxide. Rotation of either aldehyde or carbonyl oxide in the solvent cage leads to an antiparallel alignment of molecular dipole moments and dipole-dipole attraction.

  1. Biodegradation of cycloalkane carboxylic acids in oil sand tailings

    International Nuclear Information System (INIS)

    The biodegradation of both an n-alkane and several carboxylated cycloalkanes was examined experimentally within tailings produced by the extraction of bitumen from the Athabasca oil sands. The carboxylated cycloalkanes examined were structurally similar to naphthenic acids that have been associated with the acute toxicity of oil sand tailings. The biodegradation potential of naphthenic acids was estimated by determining the biodegradation of both the carboxylated cycloalkanes and hexadecane in oil sand tailings. Carboxylated cycloalkanes were biodegraded within oil sands tailings, although compounds with methyl substitutions on the cycloalkane ring were more resistant to microbial degradation. Microbial activity against hexadecane and certain carboxylated cycloalkanes was found to be nitrogen and phosphorus limited. 21 refs., 3 refs., 1 tab

  2. In vitro assessment of potential intestinal absorption of some phenolic families and carboxylic acids from commercial instant coffee samples.

    Science.gov (United States)

    López-Froilán, R; Ramírez-Moreno, E; Podio, N S; Pérez-Rodríguez, M L; Cámara, M; Baroni, M V; Wunderlin, D A; Sánchez-Mata, M C

    2016-06-15

    Coffee is one of the most consumed beverages in the world, being a source of bioactive compounds as well as flavors. Hydroxycinnamic acids, flavonols, and carboxylic acids have been studied in the samples of instant coffee commercialized in Spain. The studies about contents of food components should be complemented with either in vitro or in vivo bioaccessibility studies to know the amount of food components effectively available for functions in the human body. In this sense, a widely used in vitro model has been applied to assess the potential intestinal absorption of phenolic compounds and organic acids. The contents of hydroxycinnamic acids and flavonols were higher in instant regular coffee samples than in the decaffeinated ones. Bioaccessible phenolic compounds in most analyzed samples account for 20-25% of hydroxycinnamic acids and 17-26% of flavonols. This could mean that a great part of them can remain in the gut, acting as potential in situ antioxidants. Quinic, acetic, pyroglutamic, citric and fumaric acids were identified in commercial instant coffee samples. Succinic acid was found in the coffee blend containing chicory. All carboxylic acids showed a very high bioaccessibility. Particularly, acetic acid and quinic acid were found in higher contents in the samples treated with the in vitro simulation of gastrointestinal processes, compared to the original ones, which can be explained by their cleavage from chlorogenic acid during digestion. This is considered as a positive effect, since quinic acid is considered as an antioxidant inducer. PMID:27191052

  3. Effect of Concentration of Structurally-Different Carboxylic Acids on Growth and Aggregation of Calcium Oxalate in Gel Systems

    Institute of Scientific and Technical Information of China (English)

    DENG,Sui-Ping; OUYANG,Jian-Ming

    2007-01-01

    The effect of concentration of structurally-different carboxylic acids such as ethylene diamine tetraacetic acid (H4edta), citric acid (H3cit), tartaric acid (H2tart), and acetic acid (HOAc) on growth and aggregation of calcium oxalate (CaOxa) in gel systems was comparatively investigated. H2tart and H3cit could change the morphology of calcium oxalate monohydrate (COM) and induce the formation of calcium oxalate dihydrate (COD). H4edta could induce the formation of COD at a lower concentration of 0.33 mmol/L and have the strongest ability to inhibit aggregation of COM. HOAc inhibited COM aggregation only at a higher concentration than 500 mmol/L. With increasing the number of carboxylic groups in an acid or increasing the concentration of carboxylic acid, the capacity of this acid to induce COD formation and to inhibit growth and aggregation of COM crystals increased. That is, this capacity followed the order: H4edta>H3cit>H2tart>>HOAc. The result in this work suggested that the presence of H3cit and H2tart in urine played a role in the natural defense against stone formation.

  4. Ambient Ionic Liquids Used in the Reduction ofAldehydes and Ketones

    Institute of Scientific and Technical Information of China (English)

    Dan Qian XU; Shu Ping LUO; Bao You LIU; Zhen Yuan XU; Yin Chu SHEN

    2004-01-01

    The sodium borohydride reduction of aldehydes and ketones to corresponding alcohols has been accomplished via the use of ionic liquids. The alcohols are easily obtained with excellent yields and the ionic liquid BMImBF4 could be reused.

  5. Uncatalyzed Condensation Reactions between Aromatic Aldehydes and Thiobarbituric Acid in Water

    Institute of Scientific and Technical Information of China (English)

    Bing Qin YANG; Jun LU; Min TIAN

    2003-01-01

    A series of 5-arylidene thiobarbituric acids were prepared from aromatic aldehydes and thiobarbituric acid in water without catalyst conditions in good yields. The structures were characterized by elemental analysis, IR and 1H NMR spectra.

  6. Synthesis of vinyl boronates from aldehydes by a practical boron-Wittig reaction.

    Science.gov (United States)

    Coombs, John R; Zhang, Liang; Morken, James P

    2015-04-01

    A highly stereoselective boron-Wittig reaction between stable and readily accessible 1,1-bis(pinacolboronates) and aldehydes furnishes a variety of synthetically useful di- and trisubstituted vinyl boronate esters. PMID:25799147

  7. Study on physico-chemical properties of dialdehyde yam starch with different aldehyde group contents

    International Nuclear Information System (INIS)

    Dialdehyde yam starches (DASs) are prepared and characterized. Compared with native starch, viscosity average molecular weight of DASs decreases, and the extent of degradation depends on content of the aldehyde groups. Fourier transform infrared (FT-IR) spectra confirm that the characteristic peak for C=O group at 1732 cm-1 is enhanced with the increasing of content of the aldehyde groups. Scanning electron microscopy (SEM) micrographs show that the surface of starch granules becomes wrinkled. X-ray diffraction (XRD) patterns clearly indicate that their crystallinity decreases with the increasing content of the aldehyde groups before they become amorphous at higher oxidation states. The experimental results of thermogravimetric analysis (TGA) show that DASs have poor stability as compared to native starch. With the increase in content of the aldehyde groups, the thermal stability of DAS declines gradually. According to the results of differential scanning calorimetry (DSC), gelatinization temperature (To and Tp) of DASs are increased, whereas the gelatinization enthalpy decreased.

  8. Organocatalytic enantioselective Michael addition reactions of fluoromalonates with α,β-unsaturated aldehydes

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    A new organocatalytic enantioselective Michael addition of α-fluoromalonate to enals has been developed.The process is efficiently catalyzed by readily available chiral diphenylpyrolinol TES ether under mild reaction conditions to afford versatile highly enantioenriched fluorinated aldehydes.

  9. The mechanism for the rhodium-catalyzed decarbonylation of aldehydes: A combined experimental and theoretical study

    DEFF Research Database (Denmark)

    Fristrup, Peter; Kreis, Michael; Palmelund, Anders; Norrby, Per-Ola; Madsen, Robert

    2008-01-01

    The mechanism for the rhodium-catalyzed decarbonylation of aldehydes was investigated by experimental techniques (Hammett studies and kinetic isotope effects) and extended by a computational study (DFT calculations). For both benzaldehyde and phenyl acetaldehyde derivatives, linear Hammett plots...

  10. Tetrabutylammonium fluoride promoted regiospecific reactions of trimethylsilyl-o-carborane with aldehydes

    International Nuclear Information System (INIS)

    Trimethylsilyl-o-carborane serves as o-carborane carbanion upon fluoride ion promoted reaction with carbonyl compounds. Thus, in the presence of tetrabutylammonium fluoride, trimethylsilyl-o-carborane undergoes facile, unprecedented, carbodesilylation with aromatic and aliphatic aldehydes. (author)

  11. Aldehyde dehydrogenase inhibition as a pathogenic mechanism in Parkinson disease.

    Science.gov (United States)

    Fitzmaurice, Arthur G; Rhodes, Shannon L; Lulla, Aaron; Murphy, Niall P; Lam, Hoa A; O'Donnell, Kelley C; Barnhill, Lisa; Casida, John E; Cockburn, Myles; Sagasti, Alvaro; Stahl, Mark C; Maidment, Nigel T; Ritz, Beate; Bronstein, Jeff M

    2013-01-01

    Parkinson disease (PD) is a neurodegenerative disorder particularly characterized by the loss of dopaminergic neurons in the substantia nigra. Pesticide exposure has been associated with PD occurrence, and we previously reported that the fungicide benomyl interferes with several cellular processes potentially relevant to PD pathogenesis. Here we propose that benomyl, via its bioactivated thiocarbamate sulfoxide metabolite, inhibits aldehyde dehydrogenase (ALDH), leading to accumulation of the reactive dopamine metabolite 3,4-dihydroxyphenylacetaldehyde (DOPAL), preferential degeneration of dopaminergic neurons, and development of PD. This hypothesis is supported by multiple lines of evidence. (i) We previously showed in mice the metabolism of benomyl to S-methyl N-butylthiocarbamate sulfoxide, which inhibits ALDH at nanomolar levels. We report here that benomyl exposure in primary mesencephalic neurons (ii) inhibits ALDH and (iii) alters dopamine homeostasis. It induces selective dopaminergic neuronal damage (iv) in vitro in primary mesencephalic cultures and (v) in vivo in a zebrafish system. (vi) In vitro cell loss was attenuated by reducing DOPAL formation. (vii) In our epidemiology study, higher exposure to benomyl was associated with increased PD risk. This ALDH model for PD etiology may help explain the selective vulnerability of dopaminergic neurons in PD and provide a potential mechanism through which environmental toxicants contribute to PD pathogenesis. PMID:23267077

  12. Coniferyl Aldehyde Ameliorates Radiation Intestine Injury via Endothelial Cell Survival

    International Nuclear Information System (INIS)

    Cancer treatments related gastrointestinal toxicity has also been recognized as a significant economic burden. Especially, extensive apoptosis of microvascular endothelial cell of the lamina propria is the primary lesion initiating intestinal radiation damage after abdominal radiation therapy. Coniferyl aldehyde (CA) is phenolic compounds isolated from cork stoppers, and one of the major pyrolysis products of lignin. Shi H. was support for the empirical use of CA as a medicinal food for cardiovascular diseases. CA has positive effect in broad way but there is no consequence in radiation induced intestine damage. Here, we investigate effect of CA on small intestine after abdominal IR to mice in this study. In this study, CA increased the survival rate in C3H mice against 13.5 Gy abdominal IR. We found CA protects small intestine via preventing endothelial cell apoptosis and enhancing their angiogenic activity. CA also showed protective effect on crypt cell survival. Endothelial cell survival may affect crypt cell protection against IR. From this data, we concluded that CA is effective for protection against abdominal radiation injury. CA could ameliorate side-effect of radiation therapy

  13. Coniferyl Aldehyde Ameliorates Radiation Intestine Injury via Endothelial Cell Survival

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Ye Ji; Jung, Myung Gu; Lee, Yoonjin; Lee, Haejune [Korea Institute of Radiological and Medical Sciences, Seoul (Korea, Republic of); Lee, Yunsil [Ewha Woman' s Univ., Seoul (Korea, Republic of); Ko, Younggyu [Korea Univ., Seoul (Korea, Republic of)

    2014-05-15

    Cancer treatments related gastrointestinal toxicity has also been recognized as a significant economic burden. Especially, extensive apoptosis of microvascular endothelial cell of the lamina propria is the primary lesion initiating intestinal radiation damage after abdominal radiation therapy. Coniferyl aldehyde (CA) is phenolic compounds isolated from cork stoppers, and one of the major pyrolysis products of lignin. Shi H. was support for the empirical use of CA as a medicinal food for cardiovascular diseases. CA has positive effect in broad way but there is no consequence in radiation induced intestine damage. Here, we investigate effect of CA on small intestine after abdominal IR to mice in this study. In this study, CA increased the survival rate in C3H mice against 13.5 Gy abdominal IR. We found CA protects small intestine via preventing endothelial cell apoptosis and enhancing their angiogenic activity. CA also showed protective effect on crypt cell survival. Endothelial cell survival may affect crypt cell protection against IR. From this data, we concluded that CA is effective for protection against abdominal radiation injury. CA could ameliorate side-effect of radiation therapy.

  14. Does acute exposure to aldehydes impair pulmonary function and structure?

    Science.gov (United States)

    Abreu, Mariana de; Neto, Alcendino Cândido; Carvalho, Giovanna; Casquillo, Natalia Vasconcelos; Carvalho, Niedja; Okuro, Renata; Ribeiro, Gabriel C Motta; Machado, Mariana; Cardozo, Aléxia; Silva, Aline Santos E; Barboza, Thiago; Vasconcellos, Luiz Ricardo; Rodrigues, Danielle Araujo; Camilo, Luciana; Carneiro, Leticia de A M; Jandre, Frederico; Pino, Alexandre V; Giannella-Neto, Antonio; Zin, Walter A; Corrêa, Leonardo Holanda Travassos; Souza, Marcio Nogueira de; Carvalho, Alysson R

    2016-07-15

    Mixtures of anhydrous ethyl alcohol and gasoline substituted for pure gasoline as a fuel in many Brazilian vehicles. Consequently, the concentrations of volatile organic compounds (VOCs) such as ketones, other organic compounds, and particularly aldehydes increased in many Brazilian cities. The current study aims to investigate whether formaldehyde, acetaldehyde, or mixtures of both impair lung function, morphology, inflammatory and redox responses at environmentally relevant concentrations. For such purpose, C57BL/6 mice were exposed to either medical compressed air or to 4 different mixtures of formaldehyde and acetaldehyde. Eight hours later animals were anesthetized, paralyzed and lung mechanics and morphology, inflammatory cells and IL-1β, KC, TNF-α, IL-6, CCL2, MCP-1 contents, superoxide dismutase and catalalase activities were determined. The extra pulmonary respiratory tract was also analyzed. No differences could be detected between any exposed and control groups. In conclusion, no morpho-functional alterations were detected in exposed mice in relation to the control group. PMID:27102012

  15. Sodium borohydride removes aldehyde inhibitors for enhancing biohydrogen fermentation.

    Science.gov (United States)

    Lin, Richen; Cheng, Jun; Ding, Lingkan; Song, Wenlu; Zhou, Junhu; Cen, Kefa

    2015-12-01

    To enhance biohydrogen production from glucose and xylose in the presence of aldehyde inhibitors, reducing agent (i.e., sodium borohydride) was in situ added for effective detoxification. The detoxification efficiencies of furfural (96.7%) and 5-hydroxymethylfurfural (5-HMF, 91.7%) with 30mM NaBH4 were much higher than those of vanillin (77.3%) and syringaldehyde (69.3%). Biohydrogen fermentation was completely inhibited without detoxification, probably because of the consumption of nicotinamide adenine dinucleotide (NADH) by inhibitors reduction (R-CHO+2NADH→R-CH2OH+2NAD(+)). Addition of 30mM NaBH4 provided the reducing power necessary for inhibitors reduction (4R-CHO+NaBH4+2H2O→4R-CH2OH+NaBO2). The recovered reducing power in fermentation resulted in 99.3% recovery of the hydrogen yield and 64.6% recovery of peak production rate. Metabolite production and carbon conversion after detoxification significantly increased to 63.7mM and 81.9%, respectively. PMID:26342346

  16. Efficient Synthesis of Molecular Precursors for Para-Hydrogen-Induced Polarization of Ethyl Acetate-1-(13) C and Beyond.

    Science.gov (United States)

    Shchepin, Roman V; Barskiy, Danila A; Coffey, Aaron M; Manzanera Esteve, Isaac V; Chekmenev, Eduard Y

    2016-05-10

    A scalable and versatile methodology for production of vinylated carboxylic compounds with (13) C isotopic label in C1 position is described. It allowed synthesis of vinyl acetate-1-(13) C, which is a precursor for preparation of (13) C hyperpolarized ethyl acetate-1-(13) C, which provides a convenient vehicle for potential in vivo delivery of hyperpolarized acetate to probe metabolism in living organisms. Kinetics of vinyl acetate molecular hydrogenation and polarization transfer from para-hydrogen to (13) C via magnetic field cycling were investigated. Nascent proton nuclear spin polarization (%PH ) of ca. 3.3 % and carbon-13 polarization (%P13C ) of ca. 1.8 % were achieved in ethyl acetate utilizing 50 % para-hydrogen corresponding to ca. 50 % polarization transfer efficiency. The use of nearly 100% para-hydrogen and the improvements of %PH of para-hydrogen-nascent protons may enable production of (13) C hyperpolarized contrast agents with %P13C of 20-50 % in seconds using this chemistry. PMID:27061815

  17. Garner’s aldehyde as a versatile intermediate in the synthesis of enantiopure natural products

    Directory of Open Access Journals (Sweden)

    Mikko Passiniemi

    2013-11-01

    Full Text Available Since its introduction to the synthetic community in 1984, Garner’s aldehyde has gained substantial attention as a chiral intermediate for the synthesis of numerous amino alcohol derivatives. This review presents some of the most successful carbon chain elongation reactions, namely carbonyl alkylations and olefinations. The literature is reviewed with particular attention on understanding how to avoid the deleterious epimerization of the existing stereocenter in Garner’s aldehyde.

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

    OpenAIRE

    Singer, M E; Finnerty, W R

    1985-01-01

    The role of fatty aldehyde dehydrogenases (FALDHs) in hexadecane and hexadecanol metabolism was studied in Acinetobacter sp. strain HO1-N. Two distinct FALDHs were demonstrated in Acinetobacter sp. strain HO1-N: a membrane-bound, NADP-dependent FALDH activity induced 5-, 15-, and 9-fold by growth on hexadecanol, dodecyl aldehyde, and hexadecane, respectively, and a constitutive, NAD-dependent, membrane-localized FALDH. The NADP-dependent FALDH exhibited apparent Km and Vmax values for decyl a...

  19. Chromatographic Methods for the Analyses of 2-Halofatty Aldehydes and Chlorohydrin Species of Lysophosphatidylcholine

    OpenAIRE

    Albert, Carolyn J; Anbukumar, Dhanalakshmi S.; Messner, Maria C.; Ford, David A.

    2008-01-01

    Plasmalogens are targeted by hypohalous acids resulting in the production of 2-chlorofatty aldehydes, 2-bromofatty aldehydes and chlorohydrin species of lysophosphatidylcholine. These novel lipids have required the development of techniques for their purification and quantification. Thin layer chromatography, high performance liquid chromatography and gas chromatography of these lipids and their derivatives have provided a battery of tools for their analyses. These lipids have been quantified...

  20. Garner’s aldehyde as a versatile intermediate in the synthesis of enantiopure natural products

    OpenAIRE

    Mikko Passiniemi; Koskinen, Ari M P

    2013-01-01

    Since its introduction to the synthetic community in 1984, Garner’s aldehyde has gained substantial attention as a chiral intermediate for the synthesis of numerous amino alcohol derivatives. This review presents some of the most successful carbon chain elongation reactions, namely carbonyl alkylations and olefinations. The literature is reviewed with particular attention on understanding how to avoid the deleterious epimerization of the existing stereocenter in Garner’s aldehyde.

  1. Chronic oral exposure to the aldehyde pollutant acrolein induces dilated cardiomyopathy

    OpenAIRE

    Ismahil, Mohamed Ameen; Hamid, Tariq; Haberzettl, Petra; Gu, Yan; Chandrasekar, Bysani; Srivastava, Sanjay; Bhatnagar, Aruni; Prabhu, Sumanth D.

    2011-01-01

    Environmental triggers of dilated cardiomyopathy are poorly understood. Acute exposure to acrolein, a ubiquitous aldehyde pollutant, impairs cardiac function and cardioprotective responses in mice. Here, we tested the hypothesis that chronic oral exposure to acrolein induces inflammation and cardiomyopathy. C57BL/6 mice were gavage-fed acrolein (1 mg/kg) or water (vehicle) daily for 48 days. The dose was chosen based on estimates of human daily unsaturated aldehyde consumption. Compared with ...

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

    Science.gov (United States)

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

    2016-09-25

    Plant NAD(+)-dependent aminoaldehyde dehydrogenases (AMADHs, EC 1.2.1.19) belong to the family 10 of aldehyde dehydrogenases. They participate in the metabolism of polyamines or osmoprotectants. The enzymes are characterized by their broad substrate specificity covering ω-aminoaldehydes, aliphatic and aromatic aldehydes as well as nitrogen-containing heterocyclic aldehydes. The isoenzyme 1 from tomato (Solanum lycopersicum; SlAMADH1) oxidizes aliphatic aldehydes very efficiently and converts also furfural, its derivatives or benzaldehyde, which are present at low concentrations in alcoholic distillates such as fruit brandy. In this work, SlAMADH1 was examined as a bioanalytical tool for their detection. These aldehydes arise from fermentation processes or thermal degradation of sugars and their presence is related to health complications after consumption including nausea, emesis, sweating, decrease in blood pressure, hangover headache, among others. Sixteen samples of slivovitz (plum brandy) from local producers in Moravia, Czech Republic, were analyzed for their aldehyde content using a spectrophotometric activity assay with SlAMADH1. In all cases, there were oxidative responses observed when monitoring NADH production in the enzymatic reaction. Aldehydes in the distillate samples were also subjected to a standard determination using reversed-phase HPLC with spectrophotometric and tandem mass spectrometric detection after a derivatization with 2,4-dinitrophenylhydrazine. Results obtained by both methods were found to correlate well for a majority of the analyzed samples. The possible applicability of SlAMADH1 for the evaluation of aldehyde content in food and beverages has now been demonstrated. PMID:26703808

  3. Formation of Aldehyde and Ketone Compounds during Production and Storage of Milk Powder

    OpenAIRE

    Weijun Wang; Lanwei Zhang; Yanhua Li

    2012-01-01

    Certain aldehyde and ketone compounds can be used as indicators, at a molecular level, of the oxidized flavor of milk powder instead of sensory evaluation. This study investigated the formation of aldehyde and ketone compounds as affected by the heat-related processing and storage of milk powder. The compounds were extracted by solid phase microextraction fiber and determined using gas chromatography-mass spectrometry. In the results, higher contents of hexanal, 2-heptanone, octanal and 3-oct...

  4. DNA-Templated Polymerization of Side-Chain-Functionalized Peptide Nucleic Acid Aldehydes

    OpenAIRE

    Kleiner, Ralph E.; Brudno, Yevgeny; Birnbaum, Michael E.; Liu, David R.

    2008-01-01

    The DNA-templated polymerization of synthetic building blocks provides a potential route to the laboratory evolution of sequence-defined polymers with structures and properties not necessarily limited to those of natural biopolymers. We previously reported the efficient and sequence-specific DNA-templated polymerization of peptide nucleic acid (PNA) aldehydes. Here, we report the enzyme-free, DNA-templated polymerization of side-chain-functionalized PNA tetramer and pentamer aldehydes. We obs...

  5. Aldehyde-Tagged Zirconium Metal-Organic Frameworks: a Versatile Platform for Postsynthetic Modification.

    Science.gov (United States)

    Xi, Fu-Gui; Liu, Hui; Yang, Ning-Ning; Gao, En-Qing

    2016-05-16

    Aldehyde-tagged UiO-67-type metal-organic frameworks (MOFs) have been synthesized via the direct solvothermal method or postsynthetic ligand exchange. Various functionalities have been introduced into the MOFs via postsynthetic modification (PSM) employing C-N and C-C coupling reactions of the aldehyde tag. Tandem PSM has also been demonstrated. An amino-functionalized MOF obtained by PSM is shown to be an efficient, heterogeneous, and recyclable catalyst for Knoevenagel condensation. PMID:27136395

  6. Ambient concentrations of aldehydes in relation to Beijing Olympic air pollution control measures

    OpenAIRE

    J. C. Gong; Zhu, T.; M. Hu; L. W. Zhang; Cheng, H.; L. Zhang; Tong, J; Zhang, J.

    2010-01-01

    Aldehydes are ubiquitous constituents of the atmosphere. Their concentrations are elevated in polluted urban atmospheres. The present study was carried out to characterize three aldehydes of most health concern (formaldehyde, acetaldehyde, and acrolein) in a central Beijing site in the summer and early fall of 2008 (from June to October). Measurements were made before, during, and after the Beijing Olympics to examine whether the air pollution control measures implemented to improve Beijing's...

  7. Oxidation of Group 8 transition-Metal Hydrides and Ionic Hydrogenation of Ketones and Aldehydes

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kjell-Tore

    1996-08-01

    Transition-metal hydrides have received considerable attention during the last decades because of their unusual reactivity and their potential as homogeneous catalysts for hydrogenation and other reactions of organic substrates. An important class of catalytic processes where transition-metal hydrides are involved is the homogeneous hydrogenation of alkenes, alkynes, ketones, aldehydes, arenes and nitro compounds. This thesis studies the oxidation of Group 8 transition-metal hydrides and the ionic hydrogenation of ketones and aldehydes.

  8. Group X Aldehyde Dehydrogenases of Pseudomonas aeruginosa PAO1 Degrade Hydrazones

    OpenAIRE

    Taniyama, Kosuke; Itoh, Hideomi; Takuwa, Atsushi; Sasaki, Yasuyuki; Yajima, Shunsuke; Toyofuku, Masanori; Nomura, Nobuhiko; Takaya, Naoki

    2012-01-01

    Hydrazones are natural and synthetic compounds containing a C=N-N moiety. Here we found that the opportunistic pathogen Pseudomonas aeruginosa PAO1 produced NAD+- or NADP+-dependent hydrazone dehydrogenase (HDH), which converts hydrazones to the corresponding hydrazides and acids rather than to the simple hydrolytic product aldehydes. Gene cloning indicated that the HDH is part of the group X aldehyde dehydrogenase (ALDH) family, which is distributed among bacteria, although the physiological...

  9. Investigation of aldehyde oxidase and xanthine oxidoreductase in rainbow trout (Oncorhynchus mykiss)

    OpenAIRE

    Aburas, Omaro A Emhmed

    2014-01-01

    Molybdo-flavoenzymes (MFEs), aldehyde oxidase (AOX) and xanthine oxidoreductase (XOR) are involved in the oxidation of N-heterocyclic compounds and aldehydes, many of which are environmental pollutants, drugs and vitamins. This biotransformation generally generates more polar compounds that are more easily excreted, thus MFEs have been classed as detoxication enzymes. To date there has been scant study of the properties, substrate and inhibitor specificities of MFEs in non-mammalian vert...

  10. An Improved Protocol for the Aldehyde Olefination Reaction Using (bmim ( as Reaction Medium

    Directory of Open Access Journals (Sweden)

    Vivek Srivastava

    2013-01-01

    Full Text Available [Ru(CODCl2]/CuCl2·2H2O/LiCl catalytic system works efficiently in ionic liquid media for aldehyde olefination reaction. It offers good yield and selectivity with the added advantage of 5 times recyclability for [Ru(CODCl2] /CuCl2·2H2O/LiCl catalytic system. We also successfully reduced the reaction time from 12 hours to 9 hours for the aldehyde olefination reaction.

  11. Substrate-Directed Hydroacylation: Rh-Catalyzed Coupling of Vinyl Phenols and Non-Chelating Aldehydes

    OpenAIRE

    Murphy, Stephen K.; Bruch, Achim; Dong, Vy M.

    2014-01-01

    We report a protocol for branched-selective hydroacylation of vinylphenols with aryl, alkenyl and alkyl aldehydes. This cross-coupling yields α-aryl ketones that can be cyclized to benzofurans, and it enables access to eupomatenoid natural products in four steps or less from eugenol. Excellent reactivity and high levels of branched regioselectivity are obtained. We propose that aldehyde decarbonylation is overcome by using an anionic directing group on the olefin and a small bite-angle diphos...

  12. The pharmacology of nomegestrol acetate.

    Science.gov (United States)

    Ruan, Xiangyan; Seeger, Harald; Mueck, Alfred O

    2012-04-01

    Nomegestrol acetate (NOMAC) is a 19-norprogesterone derivative with high biological activity at the progesterone receptor, a weak anti-androgenic effect, but with no binding to estrogen, glucocorticoid or mineralocorticoid receptors. At dosages of 1.5mg/day or more, NOMAC effectively suppresses gonadotropic activity and ovulation in women of reproductive age. Hemostasis, lipids and carbohydrate metabolism remain largely unchanged. In normal and cancerous human breast cells, NOMAC has shown favorable effects on estrogen metabolism. Like natural progesterone (but in contrast to some other synthetic progestogens), it does not appear stimulate the proliferation of cancerous breast cells. While there has been some experience of the use of NOMAC in combination with estrogens as a hormone replacement therapy, most of the data on the compound are reported in the context of its inclusion as a component of a new contraceptive pill comprising 2.5mg NOMAC combined with 1.5mg estradiol. Because of its strong endometrial efficacy, and due to its high antigonadotropic activity and long elimination half-life (about 50h), the contraceptive efficacy of the new pill is maintained even when dosages are missed. Furthermore, for the first time with a monophasic 24/4 regimen containing estradiol, cyclical stability can be achieved comparable with that obtained using pills containing ethinyl estradiol and progestogens like levonorgestrel or drospirenone. The addition of NOMAC to estradiol means that the beneficial effects of estrogen are not lost, which is of especial importance in relation to the cardiovascular system. On the basis both of its pharmacology and of studies performed during the development of the NOMAC/estradiol pill, involving some 4000 women in total, good long-term tolerability can be expected for NOMAC, although its safety profile is still to be fully ascertained, as the clinical endpoint studies are yet to be completed. PMID:22364709

  13. Conversion to eslicarbazepine acetate monotherapy

    Science.gov (United States)

    French, Jacqueline; Jacobson, Mercedes P.; Pazdera, Ladislav; Gough, Mallory; Cheng, Hailong; Grinnell, Todd; Blum, David

    2016-01-01

    Objective: To assess the efficacy and safety of eslicarbazepine acetate (ESL) monotherapy. Methods: This post hoc pooled analysis of 2 randomized double-blind studies (093-045 and -046) included adults with partial-onset seizures medically uncontrolled by 1 or 2 antiepileptic drugs (AEDs). Following the baseline period (8 weeks), eligible patients were randomized 2:1 to receive ESL 1,600 mg or 1,200 mg once daily for 18 weeks; the primary endpoint was study exit by meeting predefined exit criteria (signifying worsening seizure control). In each study, treatment was considered effective if the upper 95% confidence limit for exit rate was lower than the historical control threshold (65.3%). Results: Pooled exit rates were as follows: ESL 1,600 mg = 20.6% (95% confidence interval: 15.6%–26.8%); ESL 1,200 mg = 30.8% (23.0%–40.5%). Use of 2 baseline AEDs or rescue medication, US location, epilepsy duration ≥20 years, and higher maximum baseline seizure frequency were associated with higher exit risks. Median percent reductions in standardized seizure frequency between baseline and the 18-week double-blind period were as follows: ESL 1,600 mg = 43.2%; ESL 1,200 mg = 35.7%; baseline carbamazepine use was associated with smaller reductions. Safety profiles were similar between ESL doses. Conclusions: Exit rates for ESL monotherapy (1,600 mg and 1,200 mg once daily) were lower than the historical control threshold, irrespective of baseline AED use and region, with no additional safety concerns identified. Clinical factors and location clearly influence treatment responses in conversion-to-monotherapy trials. Classification of evidence: This pooled analysis provides Class IV evidence that for adults with medically uncontrolled partial-onset seizures, ESL monotherapy is well tolerated and effective. PMID:26911639

  14. Effect of selected aldehydes on the growth and fermentation of ethanologenic Escherichia coli

    Energy Technology Data Exchange (ETDEWEB)

    Zaldivar, J.; Ingram, L.O. [Univ. of Florida, Gainesville (United States). Dept. of Microbiology and Cell Science; Martinez, A. [Univ. of Florida, Gainesville (United States). Dept. of Microbiology and Cell Science]|[Univ. Nacional Autonoma de Mexico (Mexico). Inst. de Biotecnologia

    1999-10-05

    Bioethanol production from lignocellulosic raw-materials requires the hydrolysis of carbohydrate polymers into a fermentable syrup. During the hydrolysis of hemicellulose with dilute acid, a variety of toxic compounds are produced such as soluble aromatic aldehydes from lignin and furfural from pentose destruction. In this study, the authors have investigated the toxicity of representative aldehydes (furfural, 5-hydroxymethlyfurfural, 4-hydroxybenzaldehyde, syringaldehyde, and vanillin) as inhibitors of growth and ethanol production by ethanologenic derivatives of Escherichia coli B (strains K011 and LY01). Aromatic aldyhydes were at least twice as toxic as furfural of 5-hydroxymethylfurfural on a weight basis. The toxicities of all aldehydes (and ethanol) except furfural were additive when tested in binary combinations. In all cases, combinations with furfural were unexpectedly toxic. Although the potency of these aldehydes was directly related to hydrophobicity indicating a hydrophobic site of action, none caused sufficient membrane damage to allow the leakage of intracellular magnesium even when present at sixfold the concentrations required for growth inhibition. Of the aldehydes tested, only furfural strongly inhibited ethanol production in vitro. A comparison with published results for other microorganisms indicates that LY01 is equivalent or more resistant than other biocatalysts to the aldehydes examined in this study.

  15. [Fatty aldehydes of the plasmalogenic form of phosphatidylethanolamine in the vertebrate brain].

    Science.gov (United States)

    Kruglova, E E

    1979-01-01

    Studies have been made on the composition of fatty aldehydes of plasmalogen form of ethanolamine phospholipid in the brain of 28 fish species (13 cartilaginous and 15 teleost species, exhibiting different level of organization of the nervous system, marine and freshwater, dwelling in different habitats), as well as in the brain of other vertebrates. It was found that in all primitive species of cartilaginous fish high degree of unsaturation of fatty aldehydes is observed; in higher species the degree of unsaturation is much lower. The highest degree of unsaturation of fatty aldehydes was demonstrated for abyssal species of cartilaginous and teleost fishes. In warm-water species which dwell in the upper layers, unlike all other fishes investigated, almost all fatty aldehydes are saturated. The ratio of unsaturated and saturated fatty aldehydes in fish brain depends on the entity of phylogenetic and ecological factors. Studies on other vertebrates show that in warm-blooded animals saturated fatty aldehydes predominate, whereas in cold-blooded-unsaturated ones are more abundant. PMID:314210

  16. Accurate determination of aldehydes in amine catalysts or amines by 2,4-dinitrophenylhydrazine derivatization.

    Science.gov (United States)

    Barman, Bhajendra N

    2014-01-31

    Carbonyl compounds, specifically aldehydes, present in amine catalysts or amines are determined by reversed-phase liquid chromatography using ultraviolet detection of their corresponding 2,4-dinitrophenylhydrazones. The primary focus has been to establish optimum conditions for determining aldehydes accurately because these add exposure concerns when the amine catalysts are used to manufacture polyurethane products. Concentrations of aldehydes determined by this method are found to vary with the pH of the aqueous amine solution and the derivatization time, the latter being problematic when the derivatization reaction proceeds slowly and not to completion in neutral and basic media. Accurate determination of aldehydes in amines through derivatization can be carried out at an effective solution pH of about 2 and with derivatization time of 20min. Hydrochloric acid has been used for neutralization of an amine. For complete derivatization, it is essential to protonate all nitrogen atoms in the amine. An approach for the determination of an adequate amount of acid needed for complete derivatization has been described. Several 0.2M buffer solutions varying in pH from 4 to 8 have also been used to make amine solutions for carrying out derivatization of aldehydes. These solutions have effective pHs of 10 or higher and provide much lower aldehyde concentrations compared to their true values. Mechanisms for the formation of 2,4-dinitrophenylhydrazones in both acidic and basic media are discussed. PMID:24411140

  17. Ion-exclusion chromatographic separations of C1-C6 aliphatic carboxylic acids on a sulfonated styrene-divinylbenzene co-polymer resin column with 5-methylhexanoic acid as eluent.

    Science.gov (United States)

    Ohta, Kazutoku; Towata, Atsuya; Ohashi, Masayoshi

    2003-05-16

    The application of C7 aliphatic carboxylic acids (heptanoic, 2-methylhexanoic, 5-methylhexanoic and 2,2-dimethyl-n-valeric acids) as eluents in ion-exclusion chromatography with conductimetric detection for C1-C6 aliphatic carboxylic acids (formic, acetic, propionic, isobutyric, butyric, isovaleric, valeric, isocaproic and caproic acids) was carried out using a highly sulfonated styrene-divinylbenzene co-polymer resin (TSKgel SCX) in the H+ form as a stationary phase. When using 0.05 mM sulfuric acid at pH 4.0 as the eluent, peak shapes of hydrophobic carboxylic acids (isovaleric, valeric, isocaproic and caproic acids) were tailed strongly. In contrast, when using 1 mM these C7 carboxylic acids at pH ca. 4 as the eluents, although system peaks (vacant peaks) corresponding to these C7 carboxylic acids appeared, peak shapes of these hydrophobic acids were improved drastically. Excellent simultaneous separation and relatively high sensitive conductimetric detection for these C1-C6 aliphatic carboxylic acids were achieved in 25 min on the TSKgel SCX column (150 x 6 mm I.D.) using 1 mM 5-methylhexanoic acid at pH 4.0 as the eluent. PMID:12830882

  18. Mafenide acetate allergy presenting as recurrent chondritis.

    Science.gov (United States)

    Pickus, Evan J; Lionelli, Gerald T; Charles, E Woodall; Korentager, Richard A

    2002-02-01

    Acute chondritis has a strong predilection for recurrence. Mafenide acetate has been implicated in causing reactions that mimic this condition; however, these hypersensitivity reactions lack fever, fluctuance, and pain. The authors report a case of mafenide acetate allergy presenting as recurrent chondritis in a patient who had previously been treated successfully for this condition. In this patient, the allergic response resolved within 3 days after cessation of mafenide acetate. If unappreciated, it may have led to unnecessary operative intervention. Therefore, auricular edema and erythema, without fever, fluctuance, and pain, must be recognized by surgeons as a possible mafenide acetate allergy and must be considered in the differential diagnosis for patients who present with recurrent acute suppurative chondritis. PMID:11910229

  19. Qualitative analysis of some carboxylic acids by ion-exclusion chromatography with atmospheric pressure chemical ionization mass spectrometric detection.

    Science.gov (United States)

    Helale, Murad I H; Tanaka, Kazuhiko; Taoda, Hiroshi; Hu, Wenzhi; Hasebe, Kiyoshi; Haddad, Paul R

    2002-05-17

    A simple, selective and sensitive method for the determination of carboxylic acids has been developed. A mixture of formic, acetic, propionic, valeric, isovaleric, isobutyric, and isocaproic acids has been separated on a polymethacrylate-based weak acidic cation-exchange resin (TSK gel OA pak-A) based on an ion-exclusion chromatographic mechanism with detection using UV-photodiode array, conductivity and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). A mobile phase consisting of 0.85 mM benzoic acid in 10% aqueous methanol (pH 3.89) was used to separate the above carboxylic acids in about 40 min. For LC-MS, the APCI interface was used in the negative ionization mode. Linear plots of peak area versus concentration were obtained over the range 1-30 mM (r2=0.9982) and 1-30 mM (r2=0.9958) for conductimetric and MS detection, respectively. The detection limits of the target carboxylic acids calculated at S/N=3 ranged from 0.078 to 2.3 microM for conductimetric and photometric detection and from 0.66 to 3.82 microM for ion-exclusion chromatography-APCI-MS. The reproducibility of retention times was 0.12-0.16% relative standard deviation for ion-exclusion chromatography and 1.21-2.5% for ion-exclusion chromatography-APCI-MS. The method was applied to the determination of carboxylic acids in red wine, white wine, apple vinegar, and Japanese rice wine. PMID:12108651

  20. Nomegestrol acetate/estradiol: in oral contraception.

    Science.gov (United States)

    Yang, Lily P H; Plosker, Greg L

    2012-10-01

    Nomegestrol acetate/estradiol is a combined oral contraceptive with approval in many countries. This fixed-dose combination tablet contains nomegestrol acetate, a highly selective progestogen, and estradiol, a natural estrogen. It is the first monophasic combined oral contraceptive to contain estradiol, and is taken in 28-day cycles, consisting of 24 active therapy days with 4 placebo days (i.e. 24/4-day cycles). In two large, 1-year, randomized, open-label, multicentre, phase III trials in healthy adult women (aged 18-50 years), nomegestrol acetate/estradiol was at least as effective as drospirenone/ethinylestradiol as contraceptive therapy, as the pregnancy rates in women aged 18-35 years (primary efficacy population) in terms of the Pearl Index (primary endpoint) were numerically lower with nomegestrol acetate/estradiol, although the between-group difference was not statistically significant. In both trials, nomegestrol acetate/estradiol was given in a 24/4-day cycle, and drospirenone/ethinylestradiol was given in a 21/7-day cycle. The criteria for using condoms in case of forgotten doses were less stringent in the nomegestrol acetate/estradiol group than in the drospirenone/ethinylestradiol group. Nomegestrol acetate/estradiol therapy for up to 1 year was generally well tolerated in healthy adult women, with an acceptable tolerability profile in line with that expected for a combined oral contraceptive. The most commonly reported adverse events were acne and abnormal withdrawal bleeding (most often shorter, lighter or absent periods). Overall, compared with drospirenone/ethinylestradiol, nomegestrol acetate/estradiol appeared to be associated with less favourable acne-related outcomes, and shorter, lighter or absent periods. PMID:22950535

  1. Health-Beneficial Phenolic Aldehyde in Antigonon leptopus Tea

    Directory of Open Access Journals (Sweden)

    Vanisree Mulabagal

    2011-01-01

    Full Text Available Tea prepared from the aerial parts of Antigonon leptopus is used as a remedy for cold and pain relief in many countries. In this study, A. leptopus tea, prepared from the dried aerial parts, was evaluated for lipid peroxidation (LPO and cyclooxygenase (COX-1 and COX-2 enzyme inhibitory activities. The tea as a dried extract inhibited LPO, COX-1 and COX-2 enzymes by 78%, 38% and 89%, respectively, at 100 g/mL. Bioassay-guided fractionation of the extract yielded a selective COX-2 enzyme inhibitory phenolic aldehyde, 2,3,4-trihydroxy benzaldehyde. Also, it showed LPO inhibitory activity by 68.3% at 6.25 g/mL. Therefore, we have studied other hydroxy benzaldehydes and their methoxy analogs for LPO, COX-1 and COX-2 enzymes inhibitory activities and found that compound 1 gave the highest COX-2 enzyme inhibitory activity as indicated by a 50% inhibitory concentration (IC50 at 9.7 g/mL. The analogs showed only marginal LPO activity at 6.25 g/mL. The hydroxy analogs 6, 7 and 9 showed 55%, 61% and 43% of COX-2 inhibition at 100 g/mL. However, hydroxy benzaldehydes 3 and 12 showed selective COX-1 inhibition while compounds 4 and 10 gave little or no COX-2 enzyme inhibition at 100 g/mL. At the same concentration, compounds 14, 21 and 22 inhibited COX-1 by 83, 85 and 70%, respectively. Similarly, compounds 18, 19 and 23 inhibited COX-2 by 68%, 72% and 70%, at 100 g/mL. This is the first report on the isolation of compound 1 from A. leptopus tea with selective COX-2 enzyme and LPO inhibitory activities.

  2. Demand boom boosts ethyl, butyl acetate

    International Nuclear Information System (INIS)

    US ethyl and butyl acetate markets are being described as 'extremely tight.' One major domestic producer is 'in a sold-out position' and has 'gone on sales control' with respect to these two products. Producers say that sales of both ethyl and butyl acetate have increased during the past year, and industry observers say they expect to see an April 1 price initiative of 2 cts to 3 cts/lb, and possibly a second increase in October. While one producer suggests that this market strength could be 'a sign that the coatings industry is turning around,' most agree that reformulation is the principal driver of growth. Ethyl acetate is said to be replacing methyl ethyl ketone in many formulations, while butyl acetate and butyl acetate blends are substituting for methyl isobutyl ketone. In addition, both ethyl and butyl acetate work as substitutes for xylene and toluene in certain applications. In an effort to conform to the requirements of the Clean Air Act of 1990 and to cooperate with the Environmental Protection Agency's 33/50 voluntary emissions reduction program, coatings manufacturers are moving as quickly as possible to eliminate solvents from their products. And although solvents as a whole will eventually see a dramatic decline in consumption, the temporary beneficiaries of reformulation will be certain of the oxygenated solvents, says Jeff Back, business manager at Kline ampersand Co

  3. Quantum mechanics and molecular dynamics simulations of complexation of alkaline-earth and lanthanide cations by poly-amino-carboxylate ligands

    International Nuclear Information System (INIS)

    Molecular dynamics (MD) simulations on lanthanide(III) and alkaline-earth(II) complexes with poly-amino-carboxylates (ethylene-diamino-tetra-acetate EDTA4-, ethylene-diamino-tri-acetate-acetic acid EDTA(H)3-, tetra-aza-cyclo-dodecane-tetra-acetate DOTA4-, methylene-imidine-acetate MIDA2-) are reported. First, a consistent set of Lennard-Jones parameters for La3+, Eu3+ and Lu3+ cations has been derived from free energy calculations in aqueous solution. Observed differences in hydration free energies, coordination distances and hydration numbers are reproduced. Then, the solution structures of 1:1 complexes of alkaline-earth and/or lanthanide cations with EDTA4-, EDTA(H)3-, DOTA4- and 1:2 complexes of lanthanide cations with MIDA2- were studied by MD in water. In addition, free energy calculations were performed to study, for each ligand, the relative thermodynamic stabilities of complexes with Ca2+ vs Sr2+ and vs Ba2+ on the one hand, and with La3+ vs Eu3+ and vs Lu3+ on the other hand. Model does not take into account explicitly polarization and charge transfer. However, the results qualitatively agree with experimental complexation data (structure and selectivities). (author)

  4. Novel Polymers with a High Carboxylic Acid Loading

    DEFF Research Database (Denmark)

    Thomsen, Anders Daugaard; Malmström, Eva; Hvilsted, Søren

    2006-01-01

    ABSTRACT: Click chemistry has been used to prepare a range of novel polymers with pendant carboxylic acid side groups. Four azido carboxylic acids, either mono- or difunctional and aliphatic or aromatic, have been prepared and thoroughly characterized. Extensive model reactions with 1-ethyl-4......-hydroxybenzene, the simplest model for poly(4-hydroxystyrene), and the four azido carboxylic acids have been conucted to establish the proper reaction conditions and provide an analytical frame for the corresponding polymers. Poly(4-hydroxystyrene) moieties in three different polymers—poly (4-hydroxystyrene......), poly(4-hydroxystyrene-co-methyl methacrylate), and poly(4-hydroxy- styrene-b-styrene)-----have been quantitatively transformed into oxypropynes by the use of either Williamson nr Mitsunobu strategies and subsequently reacted with the azido carboxylic acids. Detailed differential scanning calorimetry...

  5. Selective carboxyl methylation of structurally altered calmodulins in Xenopus oocytes

    International Nuclear Information System (INIS)

    The eucaryotic protein carboxyl methyltransferase specifically modifies atypical D-aspartyl and L-isoaspartyl residues which are generated spontaneously as proteins age. The selectivity of the enzyme for altered proteins in intact cells was explored by co-injecting Xenopus laevis oocytes with S-adenosyl-L-[methyl-3H]methionine and structurally altered calmodulins generated during a 14-day preincubation in vitro. Control experiments indicated that the oocyte protein carboxyl methyltransferase was not saturated with endogenous substrates, since protein carboxyl methylation rates could be stimulated up to 8-fold by increasing concentrations of injected calmodulin. The oocyte protein carboxyl methyltransferase showed strong selectivities for bovine brain and bacterially synthesized calmodulins which had been preincubated in the presence of 1 mM EDTA relative to calmodulins which had been preincubated with 1 mM CaCl2. Radioactive methyl groups were incorporated into base-stable linkages with recombinant calmodulin as well as into carboxyl methyl esters following its microinjection into oocytes. This base-stable radioactivity most likely represents the trimethylation of lysine 115, a highly conserved post-translational modification which is present in bovine and Xenopus but not in bacterially synthesized calmodulin. Endogenous oocyte calmodulin incorporates radioactivity into both carboxyl methyl esters and into base-stable linkages following microinjection of oocytes with S-adenosyl-[methyl-3H]methionine alone. The rate of oocyte calmodulin carboxyl methylation in injected oocytes is calculated to be similar to that of lysine 115 trimethylation, suggesting that the rate of calmodulin carboxyl methylation is similar to that of calmodulin synthesis. At steady state, oocyte calmodulin contains approximately 0.0002 esters/mol of protein, which turn over rapidly

  6. Determination of some aliphatic carboxylic acids in anaerobic digestion process waters by ion-exclusion chromatography with conductimetric detection on a weakly acidic cation-exchange resin column.

    Science.gov (United States)

    Ito, Kazuaki; Takayama, Yohichi; Ikedo, Mikaru; Mori, Masanobu; Taoda, Hiroshi; Xu, Qun; Hu, Wenzhi; Sunahara, Hiroshi; Hayashi, Tsuneo; Sato, Shinji; Hirokawa, Takeshi; Tanaka, Kazuhiko

    2004-06-11

    The determination of seven aliphatic carboxylic acids, formic, acetic, propionic, isobutyric, n-butyric, isovaleric and n-valeric acids in anaerobic digestion process waters was examined using ion-exclusion chromatography with conductimetric detection. The analysis of these biologically important carboxylic acids is necessary as a measure for evaluating and controlling the process. The ion-exclusion chromatography system employed consisted of polymethacrylate-based weakly acidic cation-exchange resin columns (TSKgel OApak-A or TSKgel Super IC-A/C). weakly acidic eluent (benzoic acid), and conductimetric detection. Particle size and cation-exchange capacity were 5 microm and 0.1 meq./ml for TSKgel OApak-A and 3 microm and 0.2 meq./ml for TSKgel Super IC-A/C, respectively. A dilute eluent (1.0-2.0 mM) of benzoic acid was effective for the high resolution and highly conductimetric detection of the carboxylic acids. The good separation of isobutyric and n-butyric acids was performed using the TSKgel Super IC-A/C column (150 mm x 6.0 mm i.d. x 2). The simple and good chromatograms were obtained by the optimized ion-exclusion chromatography conditions for real samples from mesophilic anaerobic digestors, thus the aliphatic carboxylic acids were successfully determined without any interferences. PMID:15250416

  7. Microenvironmental characteristics important for personal exposures to aldehydes in Sacramento, CA, and Milwaukee, WI

    Science.gov (United States)

    Raymer, J. H.; Akland, G.; Johnson, T. R.; Long, T.; Michael, L.; Cauble, L.; McCombs, M.

    Oxygenated additives in gasoline are designed to decrease the ozone-forming hydrocarbons and total air toxics, yet they can increase the emissions of aldehydes and thus increase human exposure to these toxic compounds. This paper describes a study conducted to characterize targeted aldehydes in microenvironments in Sacramento, CA, and Milwaukee, WI, and to improve our understanding of the impact of the urban environment on human exposure to air toxics. Data were obtained from microenvironmental concentration measurements, integrated, 24-h personal measurements, indoor and outdoor pollutant monitors at the participants' residences, from ambient pollutant monitors at fixed-site locations in each city, and from real-time diaries and questionnaires completed by the technicians and participants. As part of this study, a model to predict personal exposures based on individual time/activity data was developed for comparison to measured concentrations. Predicted concentrations were generally within 25% of the measured concentrations. The microenvironments that people encounter daily provide for widely varying exposures to aldehydes. The activities that occur in those microenvironments can modulate the aldehyde concentrations dramatically, especially for environments such as "indoor at home." By considering personal activity, location (microenvironment), duration in the microenvironment, and a knowledge of the general concentrations of aldehydes in the various microenvironments, a simple model can do a reasonably good job of predicting the time-averaged personal exposures to aldehydes, even in the absence of monitoring data. Although concentrations of aldehydes measured indoors at the participants' homes tracked well with personal exposure, there were instances where personal exposures and indoor concentrations differed significantly. Key to the ability to predict exposure based on time/activity data is the quality and completeness of the microenvironmental

  8. [Aldehyde dehydrogenase activity and level of dopamine in certain sections of the brain of rats preferring and refusing ethanol].

    Science.gov (United States)

    Kharchenko, N K

    2000-01-01

    Aldehyde dehydrogenase activity (KF 1.2.1.3) of cytosol fractions of brain structures (hypothalamus, midbrain and new cortex) as well as dophamine content in these structures were studied in comparative aspect in rats preferring and rejection ethanol. It has been shown that there were two isoforms of aldehyde dehydrogenases (aldehyde dehydrogenase 1 and aldehyde dehydrogenase 2) in cytosol fractions of all investigated brain structures of animals preferring ethanol while only aldehyde dehydrogenase 2 has been found in the new cotex of rats rejecting ethanol. Thus, aldehyde-dehydrogenase activity is higher in the animals preferring ethanol than in those ones rejecting ethanol. Content of dophamine in the rats preferring ethanol is higher than in those ones rejecting ethanol both in the hypothalamus and new cortex. Differences between the studied groups of animals can underlie the pathologic attraction to alcohol. PMID:10979563

  9. The mechanism of hydrogen peroxide-induced aerobic oxidation of alkanes in catalysis by a vanadium complex and pyrazine-2-carboxylic acid

    International Nuclear Information System (INIS)

    It was established that effective oxy generation of alkanes by oxygen of the air in acetonitrile was catalyzed by vanadate anion in the presence of pyrazine-2-carboxylic acid (PCA) and hydrogen peroxide. Alkyl hydroxy peroxide smoothly decomposing during the process with formation of conforming ketone (aldehyde) and alcohol is a primary product of the reaction. It is shown that hydroxyl radicals come into being by reaction of complex between vanadium oxo compound derivative and hydrogen peroxide in the system; decomposition of vanadium monoperoxocomplex with PCA is a limiting stage of the process, and V(4) derivative and hydro peroxyl radicals are defined as products of its decomposition. Adequate agreement of suggested kinetic model of the process with all totality of the experimental data was obtained. The constants of suggested equilibria and the constant of the rate of decomposition of vanadium monoperoxocomplex with PCA are estimated

  10. The essential activated carboxyl group of inorganic pyrophosphatase.

    Science.gov (United States)

    Avaeva, S M; Bakuleva, N P; Baratova, L A; Nazarova, T I; Fink, N Y

    1977-05-12

    1. A carboxyl group of high reactivity has been found in inorganic pyrophosphatase (pyrophosphate phosphohydrolase, EC 3.6.1.1) from yeast. This group interacts with agents which react neither with carboxyl groups of low molecular weight compounds nor with other carboxyl groups of the protein. 2. The reaction of this activated carboxyl group with inorganic phosphate, hydroxylamine, N-methyl- and O-methylhydroxylamines, and glycine methyl ester has been studied. 3. Homoserine and homoserine lactone were found in the hydrolyzate of phosphorylated and NaBH4-reduced pyrophosphatase, indicating that an aspartyl residue is phosphorylated. 4. Hydroxylamine and other nucleophilic agents cause inactivation of pyrophosphatase as a result of interaction with a carboxyl group. Both diaminobutyric and diaminopropionic acids were seen in the acid hydrolyzate of the protein treated with hydroxylamine and subjected to rearrangement in the presence of carbodiimide. 5. The ways in which the activation of a carboxyl group in the enzyme is achieved and the presumed mechanism of action of inorganic pyrophosphatase are discussed. PMID:16652

  11. A new class of efficient 4-[(nitro substituted-phenyl)-hydrazonomethyl]- 1-phenyl-1H-pyrazole-3-carboxylate derived colorimetric chemosensor for selective sensing of fluoride and other biologically important anions

    Indian Academy of Sciences (India)

    SUMAN SWAMI; ARUNAVA AGARWALA; BABITA MALIK; RAHUL SHRIVASTAVA

    2016-09-01

    A new class of efficient colorimetric chemosensors derived from 4-[(nitro substituted-phenyl)-hydrazonomethyl]-1-phenyl-1H-pyrazole-3-carboxylate have been synthesized and characterized. The synthesized receptors exhibit instant color change from yellow to dark purple along with significant bathochromicshifts when interacted with fluoride ions. The UV-Visible and ¹H NMR titration experiments revealed that 4-[(4-nitro-phenyl)-hydrazonomethyl]-1-phenyl-1H-pyrazole-3-carboxylate derivatives showed selective sensing of fluoride ions in preference to Cl⁻, Br⁻, I⁻, PF⁻⁻, HSO₄⁻, ClO₄⁻ , CH₃COO⁻ and H₂PO₄⁻ ions while 4-[2,4-dinitro-phenyl)-hydrazonomethyl]-1-phenyl-1H-pyrazole-3-carboxylate derivatives showed sensing of acetate, dihydrogen phosphate ion and fluoride ion in organic media.

  12. A new titanium biofunctionalized interface based on poly(pyrrole-3-acetic acid) coating: proliferation of osteoblast-like cells and future perspectives.

    Science.gov (United States)

    De Giglio, Elvira; Cometa, Stefania; Calvano, Cosima-Damiana; Sabbatini, Luigia; Zambonin, Pier Giorgio; Colucci, Silvia; Benedetto, Adriana Di; Colaianni, Graziana

    2007-09-01

    In recent years, many procedures based on surface modification have been suggested to improve the biocompatibility and biofunctionality of orthopedic titanium-based implants. In this contest, the development of a new titanium-based biomaterial that could be covalently modified with biologically active molecules (i.e., RGD-peptides, growth factors, etc.) able to improve osteoblasts response was investigated. The strategy followed was based on a preliminary coating of the implant material by an adherent thin polymer film to which bioactive molecules could be grafted exploiting the polymer surface chemical reactivity. In this work, we focused our attention on pyrrole-3-acetic acid (Py-3-acetic), a pyrrole with carboxylic acid substituent, whose electrosynthesis and characterization on titanium substrates were already accomplished and whose potentialities in the design of new biocompatible surfaces are well evident. As first step, the biocompatibility of the electrochemically grown PPy-3-acetic films was investigated performing in vitro tests (adhesion and proliferation) with mouse bone marrow cells. Successively, the availability and reactivity of surface carboxylic groups were tested through the grafting of an aminoacidic residue to PPy-3-acetic films. PMID:17483896

  13. Production of Bio-gasoline by Co-cracking of Acetic Acid in Bio-oil and Ethanol

    Institute of Scientific and Technical Information of China (English)

    王树荣; 王誉蓉; 蔡勤杰; 郭祚刚

    2014-01-01

    Acetic acid was selected as the model compound representing the carboxylic acids present in bio-oil. This work focuses the co-cracking of acetic acid with ethanol for bio-gasoline production. The influences of reac-tion temperature and pressure on the conversion of reactants as well as the selectivity and composition of the crude gasoline phase were investigated. It was found that increasing reaction temperature benefited the conversion of re-actants and pressurized cracking produced a higher crude gasoline yield. At 400 °C and 1 MPa, the conversion of the reactants reached over 99%and the selectivity of the gasoline phase reached 42.79%(by mass). The gasoline phase shows outstanding quality, with a hydrocarbon content of 100%.

  14. Thermodynamics of the formation of atmospheric organic particulate matter by accretion reactions—Part 1: aldehydes and ketones

    Science.gov (United States)

    Barsanti, Kelley C.; Pankow, James F.

    The term "accretion reactions" is introduced here to refer to the large collection of reactions by which atmospheric organic molecules can add mass, especially as by combination with other organic molecules. A general thermodynamic approach is developed for evaluating the tendency of atmospheric constituents (e.g., C 10 aldehydes) to undergo accretion reactions (e.g., dimerization) and thereby form less volatile molecules (e.g., aldol condensation products) that may subsequently condense and so contribute to the levels of organic particulate matter (OPM) observed in the atmosphere. As an example, gaseous compounds A and B may contribute to OPM formation by the net overall reaction A g+B g=C liq. This reaction may occur according to any of three kinetic schemes. Scheme I: (1) A g+B g=C g (accretion in the gas phase): then (2) C g=C liq (condensation of the accretion product); Scheme II: (1) B g=B liq (condensation of B); then (2) A g+B liq=C liq (heterogeneous accretion reaction of gaseous A with condensed B); or Scheme III: (1) A g+B g=A liq+B liq (condensation of A and B); then (2) A liq+B liq=C liq (accretion of A with B within the PM phase). For all three schemes, the net overall reaction remains A g+B g=C liq. The overall thermodynamic tendency of the net reaction remains the same regardless of the actual predominating kinetic mechanism. If an accretion reaction between two atmospheric components is to produce significant new OPM, appreciable amounts of the product C must form, and the vapor pressure of C must be relatively low so that a significant proportion of C can condense into the multicomponent liquid OPM phase. This study considers the thermodynamics of accretion reactions of atmospheric aldehydes including: (a) hydration, polymerization (i.e., oligomer formation), hemiacetal/acetal formation; and (b) aldol condensation. It was concluded regarding OPM formation that: (1) the reactions in the first group are not thermodynamically favored, either in the

  15. Toxicity of polyunsaturated aldehydes of diatoms to Indo-Pacific bioindicator organism Echinometra mathaei.

    Science.gov (United States)

    Sartori, Davide; Gaion, Andrea

    2016-01-01

    Although it is well known suitability of early developmental stages of sea urchin as recommended model for pollutant toxicity testing, little is known about the sensitivity of Indo-Pacific species Echinometra mathaei to polyunsaturated aldehydes. In this study, the effect of three short chain aldehydes, 2,4-decadienal (DD), 2,4-octadienal (OD) and 2,4-heptadienal (HD), normally found in many diatoms, such as Skeletonema costatum, Skeletonema marinoi and Thalassiosira rotula, was evaluated on larval development of E. mathaei embryos. Aldehydes affected larval development in a dose-dependent manner, in particular HD>OD>DD; the results of this study highlighted the higher sensitivity of this species toward aldehydes compared with data registered for other sea urchin species. In comparison with studies reported in the literature, contrasting results were observed during our tests; therefore, an increasing toxic effect was registered with decreasing the chain length of aldehydes. This work could provide new insights in the development of new toxicological assays toward most sensitive species. PMID:25945412

  16. Surviving environmental stress: the role of betaine aldehyde dehydrogenase in marine crustaceans

    Directory of Open Access Journals (Sweden)

    NA Stephens-Camacho

    2015-02-01

    Full Text Available Betaine aldehyde dehydrogenase (BADH belongs to the aldehyde dehydrogenases (ALDH family, an ancestral group of enzymes responsible for aldehyde detoxification in several organisms. The BADH enzyme catalyzes the irreversible oxidation of betaine aldehyde to glycine betaine (GB an important osmoptrotector and osmoregulator accumulated in response to cellular osmotic stress. The BADH enzymes have been extensively described in terrestrial organisms, but information in marine crustaceans remains scarce. Research on crustacean stress-adaptive capacity to environmental stressors relates GB accumulation in response to salinity variations. Although GB de novo synthesis is confirmed on crustaceans, its metabolic pathways and regulation mechanism are unexplored. In this work, the state of the knowledge of betaine aldehyde dehydrogenase enzymes in marine crustaceans is summarized, as a mechanism to overcome the deleterious effects of changes in temperature, salinity and dissolved oxygen concentration in seawater. The purpose of this review is to provide a more comprehensive overview to set the basis for exploring novel functions and properties of BADHs on the response of crustaceans to environmental stress.

  17. Studies of the enzymatic oxidation of proline and pyrroline-5-carboxylate in mammalian mitochondria

    International Nuclear Information System (INIS)

    The two-step oxidation of proline to glutamate in vivo is catalyzed unidirectionally by the enzymes proline oxidase (E.C. 1.5.99.8) and pyrroline-5-carboxylate (P5C) dehydrogenase (E.C. 1.5.1.12). Attempts were made to purify both proteins from rat liver. In the case of proline oxidase, an integral protein of the inner mitochondrial membrane, a number of detergents were used in efforts to solubilize active free enzyme. Detergent-treated fractions were subjected to gel permeation and other chromatographic procedures, and proline oxidase was found as part of a large particle which could not be purified. Accurate kinetic analysis of the enzyme using spectrophotometric techniques was difficult due to interference from assay components. A radiochemical assay was developed which directly measured the production of radiolabeled glutamate from P5C. The compounds were separated by cation-exchange chromatography. This assay was used to screen rat tissues for activity. Western blot analysis utilizing a polyclonal rabbit anti-rat antiserum suggests the two proteins may immunocrossreact. Kinetic analysis of these enzymes using semialdehydes and other aldehydes as substrates show a similar general pattern of substrate specificity, but the rate enzyme appears to be more specific for P5C. Aliphatic semialdehydes, closely analogous in structure to P5C, are commercially unavailable. A colorimetric assay was developed to accurately quantitate semialdehydes after synthesis. This assay is dependent upon oxidation of a covalent adduct of semialdehyde with 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole

  18. Acetylation of Starch with Vinyl Acetate in Imidazolium Ionic Liquids and Characterization of Acetate Distribution

    Science.gov (United States)

    Starch was acetylated with vinyl acetate in different 1-butyl-3-methylimidazolium (BMIM) salts as solvent in effort to produce starches with different acetylation patterns. Overall degree of substitution was much higher for basic anions such as acetate and dicyanimide (dca) than for neutral anions ...

  19. Synthesis of Some Novel Compounds of Saccharinyl Acetic Acid Containing Nucleus and Evaluation of Their Biological Activities as Antimicrobial

    Directory of Open Access Journals (Sweden)

    Magda H. Abdellattif

    2016-03-01

    Full Text Available A new series of Compounds of Saccharinyl Acetic acid Containing nucleus have been prepared via an improved synthetic procedure. Where saccharinyl moiety have been introduced to 4-benzylidine-2-methyl-1,3-oxazole-5-one in position 2 , compound (3 which has been reacted with nitrogen neucleophiles as hydrazine hydrate , phenyl haydrazine, aniline, p-toludine, m,p-aminobezoic acid to get compounds from (4-6. Also the reaction of compound (3 witharomatic substrate in presence of anhydrous AlCl3 (Friedel – Crafts reaction afforded acetamide derivative (7 via the elimination of arylidine group. Moreover saccharinyl acetic acid hydrazide (8 was refluxed in acetic anhydride to give benzisothiazole derivative (9, which reacted with carbon nuleophiles (Grignard reagent to afford compound (10. But when compound (9 reacted with PCl5/POCl3 it gave compound (11 which reacted with urea and thiourea to give compound (12(a, and b. Also the condensation of compound (9 with aromatic aldehyde gave compound (13. Structures of all synthesized compounds were elucidated from I.R., 1HNMR, mass-spectroscopy, and elemental analysis.

  20. Selective esterification of non-conjugated carboxylic acids in the presence of conjugated or aromatic carboxylic acids over active carbon supported methanesulfonic acid

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Non-conjugated carboxylic acids are selectively esterified in good yields in the presence of conjugated or aromatic carboxylic acids by stirring over active carbon supported methanesulfonic acid in di-chloromethane at room temperature.

  1. Analysis of aliphatic carboxylic acids in anaerobic digestion process waters by ion-exclusion chromatography

    Institute of Scientific and Technical Information of China (English)

    Kazuaki ITO; Kazuhiko TANAKA; Jun SAKAMOTO; Kazuya NAGAOKA; Yohichi TAKAYAMA; Takashi KANAHORI; Hiroshi SUNAHARA; Tsuneo HAYASHI; Shinji SATO; Takeshi HIROKAWA

    2012-01-01

    The analysis of seven aliphatic carboxylic acids ( formic,acetic,propionic,iso-butyric,n-butyric,iso-valeric and n-valeric acid) in anaerobic digestion process waters for biogas production was examined by ion-exclusion chromatography with dilute acidic eluents (benzoic acid,perfluorobutyric acid (PFBA) and sulfuric acid) and non-suppressed conductivity/ultraviolet (UV) detection.The columns used were a styrene/divinylbenzene-based strongly acidic cation-exchange resin column ( TSKgel SCX) and a polymethacrylate-based weakly acidic cation-exchange resin column ( TSKgel Super IC-A/C ).Good separation was performed on the TSKgel SCX in shorter retention times.For the TSKgel Super IC-A/C,peak shape of the acids was sharp and symmetrical in spite of longer retention times.In addition,the mutual separation of the acids was good except for iso- and n-butyric acids.The better separation and good detection was achieved by using the two columns (TSKgel SCX and TSKgel Super IC-A/C connected in series),lower concentrations of PFBA and sulfuric acid as eluents,non-suppressed conductivity detection and UV detection at 210 nm.This analysis was applied to anaerobic digestion process waters.The chromatograms with conductivity detection were relatively simpler compared with those of UV detection.The use of two columns with different selectivities for the aliphatic carboxylic acids and the two detection modes was effective for the determination and identification of the analytes in anaerobic digestion process waters containing complex matrices.

  2. Evaluation of toxic effects of several carboxylic acids on bacterial growth by toxicodynamic modelling

    Directory of Open Access Journals (Sweden)

    Vázquez José

    2011-11-01

    Full Text Available Abstract Background Effects of organic acids on microbial fermentation are commonly tested in investigations about metabolic behaviour of bacteria. However, they typically provide only descriptive information without modelling the influence of acid concentrations on bacterial kinetics. Results We developed and applied a mathematical model (secondary model to capture the toxicological effects of those chemicals on kinetic parameters that define the growth of bacteria in batch cultures. Thus, dose-response kinetics were performed with different bacteria (Leuconostoc mesenteroides, Carnobacterium pisicola, Escherichia coli, Bacillus subtilis and Listonella anguillarum exposed at increasing concentrations of individual carboxylic acids (formic, acetic, propionic, butyric and lactic. In all bioassays the acids affected the maximum bacterial load (Xm and the maximum growth rate (vm but only in specific cases the lag phase (λ was modified. Significance of the parameters was always high and in all fermentations the toxicodynamic equation was statistically consistent and had good predictability. The differences between D and L-lactic acid effects were significant for the growth of E. coli, L. mesenteroides and C. piscicola. In addition, a global parameter (EC50,τ was used to compare toxic effects and provided a realistic characterization of antimicrobial agents using a single value. Conclusions The effect of several organic acids on the growth of different bacteria was accurately studied and perfectly characterized by a bivariate equation which combines the basis of dose-response theory with microbial growth kinetics (secondary model. The toxicity of carboxylic acids was lower with the increase of the molecular weight of these chemicals.

  3. Acetalization of carbonyl compounds with 2,2,4-trimethyl-1,3-pentanedio catalyzed by novel carbon based solid acid catalyst

    Institute of Scientific and Technical Information of China (English)

    Ling Liu; Yuechang Zhao; Shan Gan; Xuezheng Liang; Jianguo Yang; Mingyuan He

    2008-01-01

    The synthesis of 2, 4-diisopropyl-5,5-dimethyl-1,3-dioxane through the acetalization of isobutyraldehyde with 2, 2,4-trimethyl-1,3-pentanediol (TMPD) catalyzed by the novel carbon based acid was first carried out. High conversion (≥98%) and specific selectivity were obtained using the novel carbon based acid, which kept high activity after it was reused 5 times.Moreover, the catalyst could be used to catalyze the acetalization and ketalization of different aldehydes and ketones with superior yield. The yield of several products was over 90%. The novel heterogeneous catalyst has the distinct advantages of high activity, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the success of the green process greatly.

  4. Removal of dicyclohexyl acetic acid from aqueous solution using ultrasound, ozone and their combination.

    Science.gov (United States)

    Kumar, Pardeep; Headley, John; Peru, Kerry; Bailey, Jon; Dalai, Ajay

    2014-01-01

    Naphthenic acids are a complex mixture of organic components, some of which include saturated alkyl-substituted cycloaliphatic carboxylic acids and acyclic aliphatic acids. They are naturally found in hydrocarbon deposits like oil sand, petroleum, bitumen and crude oil. In this study, the oxidation of a relatively high molecular weight naphthenic acid (Dicyclohexyl acetic acid) was investigated using ozonation, ultrasonication and hydrogen peroxide alone and their combinations. Effects on oxidation of dicyclohexyl acetic acid (DAA) were measured for different concentrations of ozone ranging between 0.7 to 3.3 mg L(-1) and pH in the range 6 to 10. Ultrasonication and hydrogen peroxide alone were not effective to oxidize dicyclohexyl acetic acid, but combining ultrasonication with H2O2 had a significant effect on oxidation of dicyclohexyl acetic acid with maximum removal reaching to 84 ± 2.2% with 81 ± 2.1% reduction in chemical oxygen demand (COD). Synergistic effects were observed for combining ultrasonication with ozonation and resulted in 100% DAA removal with 98 ± 0.8% reduction in COD within 15 min at 3.3 mg L(-1) ozone concentration and 130 Watts ultrasonication power. The reaction conditions obtained for the maximum oxidation of DAA and COD removal were used for the degradation of naphthenic acids mixture extracted from oil sands process water (OSPW). The percentage oxidation of NAs mixture extracted from OSPW was 89.3 ± 1.1% in ozonation and combined ozonation and ultrasonication, but COD removal observed was 65 ± 1.2% and 78 ± 1.4% for ozonation and combined ozonation and ultrasonication treatments, respectively. PMID:25137539

  5. Kinetic and Thermodynamic Parameters for Uncatalyzed Esterification of Carboxylic Acid

    Directory of Open Access Journals (Sweden)

    Kehinde S. Bankole

    2014-06-01

    Full Text Available A fundamental study on uncatalyzed esterification of various biomass-derived aliphatic carboxylic acids with stoichiometric amount of ethanol has been investigated in an isothermal batch reactor, with the objective to convert carboxylic acids to corresponding ethyl esters and to determine both the kinetic and thermodynamic parameters. The effects of temperature on the conversion of carboxylic acid, kinetic and thermodynamic parameters have been investigated. Temperature was found to have significant effect on the rate of reaction and conversion of carboxylic acid. A simple second order reversible kinetic model was developed to determine the kinetic and thermodynamic parameters. The thermodynamic and kinetic parameters varied for uncatalyzed esterification reaction of both short-chain and long-chain carboxylic acids considered. The predicted data from the kinetic model were correlated with experimental data and the two sets of data agreed reasonably well for the uncatalyzed esterification systems. It was observed that the Van’t Hoff plot for uncatalyzed esterification of linoleic acid was non-linear curve, whereas for the Arrhenius and Eyring plots, they were linear. Additional experiments to assess the catalytic and corrosion effects of several metallic substances revealed Inconel 625 alloy, nickel wire and stainless steel materials were susceptible to corrosion problem with uncatalyzed esterification reaction at elevated reaction temperatures. However, tantalum and grade-5 titanium materials were corrosion resistance metals, suitable for similar reaction conditions and this can encourage the design of a flow reactor system. Although, uncatalyzed esterification of carboxylic acids at elevated reaction temperature is still at laboratory scale. It is our hope that the estimated kinetic and thermodynamic parameters would be the guiding tools for reactor scale-up, thus providing a new perspective into the conversion of biomass-derived carboxylic

  6. Upper-airway inflammation in relation to dust spiked with aldehydes or glucan

    DEFF Research Database (Denmark)

    Bønløkke, Jakob Hjort; Stridh, G; Sigsgaard, T.;

    2006-01-01

    Objectives Organic dust is associated with adverse effects on human airways. This study was done to investigate whether the addition of β-(1,3)-D glucan or aldehydes to office dust causes enhanced inflammation in human airways. Methods Thirty-six volunteers were exposed randomly to clean air, off...... concentration increased after exposure to dust spiked with glucan (P=0.045). Conclusions β-(1,3)-D glucan and aldehydes in office dust enhance the inflammatory effects of dust on the upper airways.......Objectives Organic dust is associated with adverse effects on human airways. This study was done to investigate whether the addition of β-(1,3)-D glucan or aldehydes to office dust causes enhanced inflammation in human airways. Methods Thirty-six volunteers were exposed randomly to clean air...

  7. Identification of candidate aldehyde oxidases from the silkworm Bombyx mori potentially involved in antennal pheromone degradation.

    Science.gov (United States)

    Pelletier, Julien; Bozzolan, Françoise; Solvar, Marthe; François, Marie-Christine; Jacquin-Joly, Emmanuelle; Maïbèche-Coisne, Martine

    2007-12-01

    Signal inactivation is a crucial step in the dynamic of olfactory process and involves various Odorant-Degrading Enzymes. In the silkworm Bombyx mori, one of the best models for studying olfaction in insects, the involvement of an antennal-specific aldehyde oxidase in the degradation of the sex pheromone component bombykal has been demonstrated over the three past decades by biochemical studies. However, the corresponding enzyme has never been characterized at the molecular level. Bioinformatic screening of B. mori genome and molecular approaches have been used to isolate several candidate sequences of aldehyde oxidases. Two interesting antennal-expressed genes have been further characterized and their putative functions are discussed in regard to their respective expression pattern and to our knowledge on aldehyde oxidase properties. Interestingly, one gene appeared as specifically expressed in the antennae of B. mori and associated in males with the bombykal-sensitive sensilla, strongly suggesting that it could encode for the previously biochemically characterized enzyme. PMID:17904312

  8. Improved automated synthesis and preliminary animal PET/CT imaging of 11C-acetate

    International Nuclear Information System (INIS)

    To study a simple and rapid automated synthetic technology of 11C-acetate (11C- AC), automated synthesis of 11C-AC was performed by carboxylation of MeMgBr/tetrahydrofuran (THF) on a polyethylene loop with 11C-CO2, followed by hydrolysis and purification on solid-phase extraction cartridges using a 11C-Choline/Methionine synthesizer made in China. A high and reproducible radiochemical yield of above 40% (decay corrected) was obtained within the whole synthesis time about 8 min from 11C-CO2. The radiochemical purity of 11C-AC was over 95%. The novel, simple and rapid on-column hydrolysis-purification procedure should adaptable to the fully automated synthesis of 11C-AC at several commercial synthesis module. 11C-AC injection produced by the automated procedure is safe and effective, and can be used for PET imaging of animals and humans. (authors)

  9. Ubiquitin-aldehyde: a general inhibitor of ubiquitin-recycling processes

    International Nuclear Information System (INIS)

    The generation and characterization of ubiquitin (Ub)-aldehyde, a potent inhibitor of Ub-C-terminal hydrolase, has previously been reported. The authors examine the action of this compound on the Ub-mediated proteolytic pathway using the system derived from rabbit reticulocytes. Addition of Ub-aldehyde was found to strongly inhibit breakdown of added 125I-labeled lysozyme, but inhibition was overcome by increasing concentrations of Ub. The following evidence shows the effect of Ub-aldehyde on protein breakdown to be indirectly caused by its interference with the recycling of Ub, leading to exhaustion of the supply of free Ub: (i) Ub-aldehyde markedly increased the accumulation of Ub-protein conjugates coincident with a much decreased rate of conjugate breakdown; (ii) release of Ub from isolated Ub-protein conjugates in the absence of ATP (and therefore not coupled to protein degradation) is markedly inhibited by Ub-aldehyde. On the other hand, the ATP-dependent degradation of the protein moiety of Ub conjugates, which is an integral part of the proteolytic process, is not inhibited by this agent; (iii) direct measurement of levels of free Ub showed a rapid disappearance caused by the inhibitor. The Ub is found to be distributed in derivatives of a wide range of molecular weight classes. It thus seems that Ub-aldehyde, previously demonstrated to inhibit the hydrolysis of Ub conjugates of small molecules, also inhibits the activity of a series of enzymes that regenerate free Ub from adducts with proteins and intermediates in protein breakdown

  10. Nephelauxetic and hypersensitive nature of neodymium(III) complexes with α-pyridyl-thiosemicarbazide and its furfural-2-aldehyde and thiophene-2-aldehyde derivatives

    International Nuclear Information System (INIS)

    A new series of octahedral Nd(III) complexes with recently synthesised α-pyridylthiosemicarbazide (C6H8N4S or 'PT'), N-(α-pyridyl)furfural-2-aldehyde-thiosemicarbazone (C11H10N4SO or 'PFT') and N-(α-pyridyl)thiophene-2-aldehyde-thiosemicarbazone (C11H10N4S2 or 'PTT'), have been isolated and characterised on the basis of their elemental analysis, magnetic and reflectance and ir spectral data revealing 'PT' as bidentate (pyridinic-N and thioketo-S) and 'PFT' and 'PTT' as tetradentate with pyridinic-N, thioketo-S, imine-N and furfuryl-O/thiophenyl-S as donor sites. Isolation and characterisation of Nd(III) complexes with 'PT', 'PFT' and 'PTT' and their nephelauxetic and hypersensitive nature are studied in order to evaluate the stereochemistry of the ligands around Nd(III) ion. (author). 12 refs., 2 tables

  11. Coenzyme A-acylating aldehyde dehydrogenase from Clostridium beijerinckii NRRL B592.

    OpenAIRE

    Yan, R T; Chen, J S

    1990-01-01

    Acetaldehyde and butyraldehyde are substrates for alcohol dehydrogenase in the production of ethanol and 1-butanol by solvent-producing clostridia. A coenzyme A (CoA)-acylating aldehyde dehydrogenase (ALDH), which also converts acyl-CoA to aldehyde and CoA, has been purified under anaerobic conditions from Clostridium beijerinckii NRRL B592. The ALDH showed a native molecular weight (Mr) of 100,000 and a subunit Mr of 55,000, suggesting that ALDH is dimeric. Purified ALDH contained no alcohol...

  12. Aryl-aldehyde formation in fungal polyketides: Discovery and characterization of a distinct biosynthetic mechanism

    OpenAIRE

    Wang, Meng; Beissner, Mirko; Zhao, Huimin

    2014-01-01

    Aryl-aldehydes are a common feature in fungal polyketides, which are considered to be exclusively generated by the R domain of non-reducing polyketide synthases (NR-PKSs). However, by cloning and heterologous expression of two cryptic NR-PKS and non-ribosomal peptide synthase (NRPS)-like genes from Aspergillus terreus in Saccharomyces cerevisiae, we discovered a distinct mechanism for aryl-aldehyde formation in which a NRPS-like protein activates and reduces an aryl-acid produced by the accom...

  13. The Impact of Single Nucleotide Polymorphisms on Human Aldehyde OxidaseS

    OpenAIRE

    Hartmann, Tobias; Terao, Mineko; Garattini, Enrico; Teutloff, Christian; Alfaro, Joshua F.; Jones, Jeffrey P.; Leimkühler, Silke

    2012-01-01

    Aldehyde oxidase (AO) is a complex molybdo-flavoprotein that belongs to the xanthine oxidase family. AO is active as a homodimer, and each 150-kDa monomer binds two distinct [2Fe2S] clusters, FAD, and the molybdenum cofactor. AO has an important role in the metabolism of drugs based on its broad substrate specificity oxidizing aromatic aza-heterocycles, for example, N1-methylnicotinamide and N-methylphthalazinium, or aldehydes, such as benzaldehyde, retinal, and vanillin. Sequencing the 35 co...

  14. Addition Reactions of Me3 SiCN with Aldehydes Catalyzed by Aluminum Complexes Containing in their Coordination Sphere O, S, and N Ligands.

    Science.gov (United States)

    Yang, Zhi; Yi, Yafei; Zhong, Mingdong; De, Sriman; Mondal, Totan; Koley, Debasis; Ma, Xiaoli; Zhang, Dongxiang; Roesky, Herbert W

    2016-05-10

    The reaction of one equivalent of LAlH2 (1; L=HC(CMeNAr)2 , Ar=2,6-iPr2 C6 H3 , β-diketiminate ligand) with two equivalents of 2-mercapto-4,6-dimethylpyrimidine hydrate resulted in LAl[(μ-S)(m-C4 N2 H)(CH2 )2 ]2 (2) in good yield. Similarly, when N-2-pyridylsalicylideneamine, N-(2,6-diisopropylphenyl)salicylaldimine, and ethyl 3-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-2-carboxylate were used as starting materials, the corresponding products LAl[(μ-O)(o-C6 H4 )CN(C5 NH4 )]2 (3), LAlH[(μ-O)(o-C4 H4 )CN(2,6-iPr2 C6 H3 )] (4), and LAl[(μ-NH)(o-C8 SH8 )(COOC2 H5 )]2 (5) were isolated. Compounds 2-5 were characterized by (1) H and (13) C NMR spectroscopy as well as by single-crystal X-ray structural analysis. Surprisingly, compounds 2-5 exhibit good catalytic activity in addition reactions of aldehydes with trimethylsilyl cyanide (TMSCN). PMID:27062461

  15. Determination of Odor Release in Hydrocolloid Model Systems Containing Original or Carboxylated Cellulose at Different pH Values Using Static Headspace Gas Chromatographic (SHS-GC Analysis

    Directory of Open Access Journals (Sweden)

    Pahn-Shick Chang

    2013-02-01

    Full Text Available Static headspace gas chromatographic (SHS-GC analysis was performed to determine the release of 13 odorants in hydrocolloid model systems containing original or regio-selectively carboxylated cellulose at different pH values. The release of most odor compounds was decreased in the hydrocolloid solutions compared to control, with the amounts of 2-propanol, 3-methyl-1-butanol, and 2,3-butanedione released into the headspace being less than those of any other odor compound in the hydrocolloid model systems. However, there was no considerable difference between original cellulose-containing and carboxylated-cellulose containing systems in the release of most compounds, except for relatively long-chain esters such as ethyl caprylate and ethyl nonanoate. The release from the original and carboxylated cellulose solutions controlled to pH 10 was significantly higher than that from solutions adjusted to pH 4 and 7 in the case of some esters (ethyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, butyl propionate, ethyl caproate and alcohols (2-propanol, 3-methyl-1-butanol, in particular, ethyl butyrate and 3-methyl-1-butanol. In contrast, the release of 2,3-butanedione from both the original and carboxylated cellulose solutions was increased at pH 4 and 7 compared to that at pH 10 by about 70% and 130%, respectively. Our study demonstrated that the release of some odorants could be changed significantly by addition of both original and carboxylated cellulose in hydrocolloid model systems, but only minor effect was observed in pH of the solution.

  16. Synthesis and Crystal Structure of 4-(4,6-Dimethoxylpyrimidin-2-yl)-3-thiourea Carboxylic Acid Ethyl Ester

    Institute of Scientific and Technical Information of China (English)

    ZHANG Yang; HUANG Jie; SONG Ji-Rong; REN Ying-Hui; XU Kang-Zhen

    2008-01-01

    4-(4,6-Dimethoxyl-pyrimidin-2-yl)-3-thiourea carboxylic acid ethyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine,potassium thiocyanate and methyl chloroformate in ethyl acetate.Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamidc at room temperature.The crystal structure was determined by X-ray diffraction analysis.Crystallographic data:C10H14N4O4S,Mr=286.31,monoclinic,space group C2/c with a=2.5309(3),b=0.67682(6),c=1.74237(19)nm,β=114.744(3)°,V=2.7106(5)nm3,Dc=1.403 g/cm3,μ=0.225mm-1,F(000)=1200,Z=8,R=0.0514 and wR=0.1529.

  17. Synthesis and Crystal Structure of 4-(4,6-dimethoxyl -pyrimidin-2-yl)-3-thiourea Carboxylic Acid Methyl Ester

    Institute of Scientific and Technical Information of China (English)

    HUANG Jie; SONG Ji-Rong; REN Ying-Hui; XU Kang-Zhen; MA Hai-Xia

    2006-01-01

    The title compound 4-(4,6-dimethoxylpyrimidin-2-yl)-3-thiourea carboxylic acid methyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamide at the room temperature. The structure was characterized by elemental analysis and IR and determined by X-ray diffraction analysis. Crystallographic data: C9H12N4O4S, Mr = 272.29, monoclinic, space group C2/m with a = 1.6672(3), b = 0.66383(12), c = 1.1617(2) nm, β = 109.275(2)°, V = 1.2136(4) nm3, Dc = 1.490 g/cm3, μ = 0.281 mm-1, F(000) = 568, Z = 4, R1 = 0.0341and wR2 = 0.1042.

  18. Kinetic mechanism of an aldehyde reductase of Saccharomyces cerevisiae that relieves toxicity of furfural and 5-hydroxymethylfurfural

    Science.gov (United States)

    An effective means of relieving the toxicity of furan aldehydes, furfural (FFA) and 5-hydroxymethylfurfural (HMF), on fermenting organisms is essential for achieving efficient fermentation of lignocellulosic biomass to ethanol and other products. Ari1p, an aldehyde reductase from Saccharomyces cerev...

  19. Aldehyde Selective Wacker Oxidations of Phthalimide Protected Allylic Amines : A New Catalytic Route to beta(3)-Amino Acids

    NARCIS (Netherlands)

    Weiner, Barbara; Baeza Garcia, Alejandro; Jerphagnon, Thomas; Feringa, Ben L.

    2009-01-01

    A new method for the synthesis of B-3-amino acids is presented. Phthalimide protected allylic amines are oxidized under Wacker conditions selectively to aldehydes using PdCl2 and CuCl or Pd(MeCN)(2)Cl(NO2) and CuCl2 as complementary catalyst systems. The aldehydes are produced in excellent yields an

  20. Aldehyde-Selective Wacker-Type Oxidation of Unbiased Alkenes Enabled by a Nitrite Co-Catalyst

    KAUST Repository

    Wickens, Zachary K.

    2013-09-13

    Breaking the rules: Reversal of the high Markovnikov selectivity of Wacker-type oxidations was accomplished using a nitrite co-catalyst. Unbiased aliphatic alkenes can be oxidized with high yield and aldehyde selectivity, and several functional groups are tolerated. 18O-labeling experiments indicate that the aldehydic O atom is derived from the nitrite salt.

  1. Pyrazine Carboxylic Acid Derivatives of Dichlorobis(Cyclopentadienyltitanium(IV

    Directory of Open Access Journals (Sweden)

    Satish Chandra Dixit

    2012-07-01

    Full Text Available Reactions of dichlorobis(cyclopentadienyltitanium(IV with pyrazine carboxylic acids viz. 2-pyrazine carboxylic acid (2-PzCH, 5-methyl-2-pyrazine carboxylic acid (MPzCH and 2,3-pyrazine dicarboxylic acid (2,3-PzDCH2 were carried out in different stoichiometric ratios. Complexes of the type Cp2Ti(2-PzCCl , Cp2Ti(2-PzC2 ,Cp2Ti(MPzCCl,Cp2Ti(MPzC2, Cp2Ti(2,3-PzDCHCl and Cp2Ti(2,3-PzDCH2 were obtained. These newly synthesized complexes were characterized on the basis of elemental analyses, electrical conductance, magnetic moment and spectral data.

  2. Pyrazine Carboxylic Acid Derivatives of Dichlorobis(Cyclopentadienyl)titanium(IV)

    OpenAIRE

    Satish Chandra Dixit; Rohit Kumar Singh

    2012-01-01

    Reactions of dichlorobis(cyclopentadienyl)titanium(IV) with pyrazine carboxylic acids viz. 2-pyrazine carboxylic acid (2-PzCH), 5-methyl-2-pyrazine carboxylic acid (MPzCH) and 2,3-pyrazine dicarboxylic acid (2,3-PzDCH2) were carried out in different stoichiometric ratios. Complexes of the type Cp2Ti(2-PzC)Cl , Cp2Ti(2-PzC)2 ,Cp2Ti(MPzC)Cl,Cp2Ti(MPzC)2, Cp2Ti(2,3-PzDCH)Cl and Cp2Ti(2,3-PzDCH)2 were obtained. These newly synthesized complexes were characterized on the basis of elemental analyse...

  3. Aging time on the aluminum basic acetate gel and its influence on the membrane permeability

    International Nuclear Information System (INIS)

    Alumina ceramic membranes are new materials with important applications in separation processes with low energy requirements, high selectivity and ability to work at high and low temperatures.The preparation of alumina ceramic membranes from hydrates or aluminum salts as precursors implies obtaining a system of controlled porosity with a suitable mechanical resistance as well as the densification of the material thanks to the stable phases remaining after the thermal treatment.The metal carboxylates are potential precursors for the deposition and the subsequent formation of oxides at low temperatures.Aluminum basic acetate gel was synthesised in this work from commercial pseudobohemite. The influence of the aging time on the composition, crystalline structure and transition temperatures of the phases on the carboxylate was studied by XRD and DTA-TG.From suspensions of this aged gel at different times alumina ceramic membranes were prepared by dipcoating on different α-Al2O3 supports and the influence of aging on the permeability of those membranes face to N2 was also studied. It was observed that this is a parameter to be considered as it determines the thickness, permeability and integrity of the membranes

  4. Vinyl acetate polymerization by ionizing radiation

    International Nuclear Information System (INIS)

    The aim of this work is the synthesis and characterization of the poly(vinyl acetate) using the ionizing radiation. Six polymerizations of vinyl acetate were carried out using three techniques of polymerization: in bulk, emulsion and solution. In the technique of solution polymerization were used two solvents, the alcohol ethyl and the methylethylketone, in two proportions 1:0.5 and 1:1 related to the monomer. The solutions were irradiated with gamma rays from a 60Co source, with dose rate between 5.25 kGy/h and 6.26 kGy/h. The polymers obtained were characterized by Fourier Transform Infrared Spectroscopy (FTIR). The glass transition temperature (Tg) was investigated by Differential Scanning Calorimeter (DSC). The molecular weight was analyzed by the technique of Gel Permeation Chromatography (GPC). Tests of density, hardness and Vicat softening temperature were carried out. The infrared spectroscopy and others results confirmed that the polymers obtained by polymerization of vinyl acetate in bulk, emulsion and solution, using ionizing radiation, really correspond at poly(vinyl acetate). (author)

  5. Formation of asymmetric cellulose acetate membranes

    NARCIS (Netherlands)

    Bokhorst, H.; Altena, F.W.; Smolders, C.A.

    1981-01-01

    Cellulose acetate membranes were prepared from casting solutions containing dioxane as a solvent and varying concentrations (up to 6%) of maleic acid as an additive. Coagulation took place in water at different temperatures. The effect of these variables on membrane structure and membrane properties

  6. Advanced Colloids Experiment (ACE-T1)

    Science.gov (United States)

    Meyer, William V.; Sicker, Ron; Brown, Dan; Eustace, John

    2015-01-01

    Increment 45 - 46 Science Symposium presentation of Advanced Colloids Experiment (ACE-T1) to RPO. The purpose of this event is for Principal Investigators to present their science objectives, testing approach, and measurement methods to agency scientists, managers, and other investigators.

  7. Effect of selected aldehydes found in the corncob hemicellulose hydrolysate on the growth and xylitol fermentation of Candida tropicalis.

    Science.gov (United States)

    Wang, Le; Tang, Pingwah; Fan, Xiaoguang; Yuan, Qipeng

    2013-01-01

    The effects of four aldehydes (furfural, 5-hydroxymethylfurfural, vanillin and syringaldehyde), which were found in the corncob hemicellulose hydrolysate, on the growth and xylitol fermentation of Candida tropicalis were investigated. The results showed that vanillin was the most toxic aldehyde for the xylitol fermentation, followed by syringaldehyde, furfural and 5-hydroxymethylfurfural. Moreover, the binary combination tests revealed that furfural amplified the toxicity of other aldehydes and the toxicities of other binary combinations without furfural were simply additive. Based on the fermentation experiments, it was demonstrated that the inhibition of aldehydes could be alleviated by prolonging the fermentation incubation, increasing the initial cell concentration, enhancing the initial pH value and minimizing the furfural levels in the hydrolysate evaporation process. The strategies that we proposed to suppress the inhibitory effects of the aldehydes successfully avoided the complicated and costly detoxifications. Our findings could be potentially adopted for the industrial xylitol fermentation from hydrolysates. PMID:23843370

  8. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, Ruth; Bhaumik, Asim [Department of Materials Science, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700032 (India); Dutta, Saikat [Department of Chemical Engineering, National Taiwan University, Taipei 10617, Taiwan (China)

    2014-11-01

    A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state {sup 13}C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N{sub 2} sorption, HR-TEM, and NH{sub 3} temperature programmed desorption-thermal conductivity detector (TPD-TCD) analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H)-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  9. Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

    Directory of Open Access Journals (Sweden)

    Ruth Gomes

    2014-11-01

    Full Text Available A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state 13C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N2 sorption, HR-TEM, and NH3 temperature programmed desorption-thermal conductivity detector (TPD-TCD analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

  10. Radiolysis of carboxylic acids adsorbed in clay minerals

    International Nuclear Information System (INIS)

    This research is aimed at studying the effect of ionizing radiation in an heterogeneous system formed by a carboxylic acid adsorbed in a clay mineral. The study is focussed to discriminate if the presence of a solid surface alters the formation and distribution of radiolytic products in relation to the radiolysis of the carboxylic acid without the surface (clay). The results showed that the radiolysis of the system clay-acid goes along a defined path rather than showing various pathways of decomposition as in the case of simple aqueous solutions. The main pathway was the decarboxylation of the target compound rather than condensation/dimerization reactions

  11. 1,2-disubstituted cyclohexane derived tripeptide aldehydes as novel selective thrombin inhibitors.

    Science.gov (United States)

    Harmat, N J; Di Bugno, C; Criscuoli, M; Giorgi, R; Lippi, A; Martinelli, A; Monti, S; Subissi, A

    1998-05-19

    A series of tripeptide arginine aldehydes was synthesized by replacement of proline with 1,2-disubstituted cyclohexane derivatives in the sequence of D-MePhe-Pro-Arg-H. Based on molecular modeling, further modification of the D-MePhe residue resulted in a potent and selective thrombin inhibitor. PMID:9871744

  12. The Condensation of Aromatic Aldehydes with Acidic Methylene Compounds in Water

    Institute of Scientific and Technical Information of China (English)

    Da Qing SHI; Jing CHEN; Qi Ya ZHUANG; Xiang Shan WANG; Hong Wen HU

    2003-01-01

    The condensation of aromatic aldehydes with acidic methylene compounds such as malononitrile, methyl cyanoacetate, cyanoacetamide, 5,5-dimethyl-1,3-cyclohexanedione, bartbituric acid and 2-thiobarbituric acid proceeded very efficiently in water in the presence of triethylbenzylammonium chloride (TEBA) and the products were isolated simply by filtration.

  13. Catalytic asymmetric allylation of aliphatic aldehydes by chiral bipyridine N,N'-dioxides

    Czech Academy of Sciences Publication Activity Database

    Hrdina, R.; Boyd, T.; Valterová, Irena; Hodačová, Jana; Kotora, Martin

    -, č. 20 (2008), s. 3141-3144. ISSN 0936-5214 Grant ostatní: GA MŠk(CZ) LC06070 Institutional research plan: CEZ:AV0Z40550506 Keywords : allylations * aldehydes * Lewis base * asymmetric catalysis * solvent effect Subject RIV: CC - Organic Chemistry Impact factor: 2.659, year: 2008

  14. Fructose derived pyridyl alcohol ligands: synthesis and application in the asymmetric diethylzinc addition to aldehydes

    Institute of Scientific and Technical Information of China (English)

    ZHOU, Yong-Gui; DAI, Li-Xin; HOU, Xue-Long

    2000-01-01

    Easily available chiral ketones were employed for the synthesis of optically active pyridyl alcohols, which were applied in the asymmetric diethylzinc addition to aldehydes, up to 89.4%e.e. was obtained using D-fructose-derived pyridyl alcohol.

  15. Aerobic oxidation of aldehydes under ambient conditions using supported gold nanoparticle catalysts

    DEFF Research Database (Denmark)

    Marsden, Charlotte Clare; Taarning, Esben; Hansen, David;

    2008-01-01

    A new, green protocol for producing simple esters by selectively oxidizing an aldehyde dissolved in a primary alcohol has been established, utilising air as the oxidant and supported gold nanoparticles as catalyst. The oxidative esterifications proceed with excellent selectivities at ambient...

  16. Perfluoroalkanesulfonamide Organocatalysts for Asymmetric Conjugate Additions of Branched Aldehydes to Vinyl Sulfones

    Directory of Open Access Journals (Sweden)

    Kosuke Nakashima

    2013-11-01

    Full Text Available Asymmetric conjugate additions of branched aldehydes to vinyl sulfones promoted by sulfonamide organocatalyst 6 or 7 have been developed, allowing facile synthesis of the corresponding adducts with all-carbon quaternary stereocenters in excellent yields with up to 95% ee.

  17. An Improved Protocol for the Pd-catalyzed α-Arylation of Aldehydes with Aryl Halides

    OpenAIRE

    Martín, Rubén; Buchwald, Stephen L.

    2008-01-01

    An improved protocol for the Pd-catalyzed α-arylation of aldehydes with aryl halides has been developed. The new catalytic system allows for the coupling of an array of substrates including challenging electron-rich aryl bromides and less reactive aryl chlorides. The utility of this method has been demonstrated in a new total synthesis of (±)-sporochnol.

  18. STUDY ON THE CARDANOL-ALDEHYDE CONDENSATION POLYMER CONTAINING BORON-NITROGEN COORDINATE BOND

    Institute of Scientific and Technical Information of China (English)

    1998-01-01

    Cardanol-aldehyde condensation polymer containing boron-nitrogen coordinate bond (CFBN) has been synthesized and characterized by IR, XPS, HPLC and DTA-TG. Its properties were also investigated. The results show that the coating film of CFBN has excellent physico-mechanical properties, good anticorrosive properties and stable at high temperature.

  19. Phosphite Ligand Modified Supported Rhodium Catalyst for Hydroformylation of Internal Olefins to Linear Aldehydes

    Institute of Scientific and Technical Information of China (English)

    LI Xian-ming; DING Yun-jie; JIAO Gui-ping; LI Jing-wei; YAN Li; ZHU He-jun

    2009-01-01

    A phosphite ligand modified heterogeneous catalyst was developed for the hydroformylation of internal olefins to linear aldehydes, which showed a high activity and high regioselectivity and could be separated easily by filtration after reaction in an autoclave. Three nanoporous silica sieves were used to investigate the influence of pore structure and shape selective performance of support on the regioselectivity to the linear products.

  20. Integrated quantification and identification of aldehydes and ketones in biological samples

    NARCIS (Netherlands)

    Siegel, David; Meinema, Anne C; Permentier, Hjalmar; Hopfgartner, Gérard; Bischoff, Rainer

    2014-01-01

    The identification of unknown compounds remains to be a bottleneck of mass spectrometry (MS)-based metabolomics screening experiments. Here, we present a novel approach which facilitates the identification and quantification of analytes containing aldehyde and ketone groups in biological samples by

  1. Kinetics of acid-catalyzed aldol condensation reactions of aliphatic aldehydes

    Science.gov (United States)

    Casale, Mia T.; Richman, Aviva R.; Elrod, Matthew J.; Garland, Rebecca M.; Beaver, Melinda R.; Tolbert, Margaret A.

    Field observations of atmospheric aerosols have established that organic compounds compose a large fraction of the atmospheric aerosol mass. However, the physical/chemical pathway by which organic compounds are incorporated into atmospheric aerosols remains unclear. The potential role of acid-catalyzed reactions of organic compounds on acidic aerosols has been explored as a possible chemical pathway for the incorporation of organic material into aerosols. In the present study, ultraviolet-visible (UV-vis) spectroscopy was used to monitor the kinetics of formation of the products of the acid-catalyzed aldol condensation reaction of a range of aliphatic aldehydes (C 2-C 8). The experiments were carried out at various sulfuric acid concentrations and a range of temperatures in order to estimate the rate constants of such reactions on sulfuric acid aerosols under tropospheric conditions. The rate constants were generally found to decrease as the chain length of the aliphatic aldehyde increased (except for acetaldehyde, which had an unusually small rate constant), increase as a function of sulfuric acid concentration as predicted by excess acidity theory, and showed normal Arrhenius behavior as a function of temperature. While the kinetic data are generally consistent with previous laboratory reports of aldehyde reactivity in various sulfuric acid media, the aldol condensation reactions involving aliphatic aldehydes do not appear fast enough to be responsible for significant transfer of organic material into atmospheric aerosols.

  2. Phenyl versus Ethyl Transfer in the Addition of Organozincs to Aldehydes: A Theoretical Study

    DEFF Research Database (Denmark)

    Rudolph, Jens; Rasmussen, Torben; Bolm, Carsten; Norrby, Per-Ola

    2003-01-01

    The dramatic improvement in diphenylzinc addition to aldehydes that is obtained by adding diethylzinc was investigated by DFT methods. The strong preference for phenyl over ethyl transfer can be understood in terms of overlap with the phenyl 31 system in the transition state (see picture). Reason...... for the high ee value in the presence of Et$-2$/Zn are discussed....

  3. Study on physico-chemical properties of dialdehyde yam starch with different aldehyde group contents

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Liming, E-mail: zhanglmd@yahoo.com.cn [Key Laboratory of Industrial Microbiology, Ministry of Education, Tianjin University of Science and Technology, Tianjin 300457 (China); Liu, Peng; Wang, Yugao [College of Biotechnology, Tianjin University of Science and Technology, Tianjin 300457 (China); Gao, Wenyuan [Key Laboratory of Industrial Microbiology, Ministry of Education, Tianjin University of Science and Technology, Tianjin 300457 (China)

    2011-01-10

    Dialdehyde yam starches (DASs) are prepared and characterized. Compared with native starch, viscosity average molecular weight of DASs decreases, and the extent of degradation depends on content of the aldehyde groups. Fourier transform infrared (FT-IR) spectra confirm that the characteristic peak for C=O group at 1732 cm{sup -1} is enhanced with the increasing of content of the aldehyde groups. Scanning electron microscopy (SEM) micrographs show that the surface of starch granules becomes wrinkled. X-ray diffraction (XRD) patterns clearly indicate that their crystallinity decreases with the increasing content of the aldehyde groups before they become amorphous at higher oxidation states. The experimental results of thermogravimetric analysis (TGA) show that DASs have poor stability as compared to native starch. With the increase in content of the aldehyde groups, the thermal stability of DAS declines gradually. According to the results of differential scanning calorimetry (DSC), gelatinization temperature (T{sub o} and T{sub p}) of DASs are increased, whereas the gelatinization enthalpy decreased.

  4. Modulation of ethanol stress tolerance by aldehyde dehydrogenase in the mycorrhizal fungus Tricholoma vaccinum.

    Science.gov (United States)

    Asiimwe, Theodore; Krause, Katrin; Schlunk, Ines; Kothe, Erika

    2012-08-01

    We report the first mycorrhizal fungal aldehyde dehydrogenase gene, ald1, which was isolated from the basidiomycete Tricholoma vaccinum. The gene, encoding a protein Ald1 of 502 amino acids, is up-regulated in ectomycorrhiza. Phylogenetic analyses using 53 specific fungal aldehyde dehydrogenases from all major phyla in the kingdom of fungi including Ald1 and two partial sequences of T. vaccinum were performed to get an insight in the evolution of the aldehyde dehydrogenase family. By using competitive and real-time RT-PCR, ald1 is up-regulated in response to alcohol and aldehyde-related stress. Furthermore, heterologous expression of ald1 in Escherichia coli and subsequent in vitro enzyme activity assay demonstrated the oxidation of propionaldehyde and butyraldehyde with different kinetics using either NAD(+) or NADP(+) as cofactors. In addition, overexpression of ald1 in T. vaccinum after Agrobacterium tumefaciens-mediated transformation increased ethanol stress tolerance. These results demonstrate the ability of Ald1 to circumvent ethanol stress, a critical function in mycorrhizal habitats. PMID:22159964

  5. Syntheses of a Flobufen Metabolite and Dapoxetine Based on Enantioselective Allylation of Aromatic Aldehydes

    Czech Academy of Sciences Publication Activity Database

    Hessler, F.; Korotvička, A.; Nečas, D.; Valterová, Irena; Kotora, M.

    2014-01-01

    Roč. 2014, č. 12 (2014), s. 2543-2548. ISSN 1434-193X Grant ostatní: GA ČR(CZ) GAP207/11/0587 Institutional support: RVO:61388963 Keywords : synthetic methods * asymmetric catalysis * organocatalysis * allylation * aldehydes * enantioselectivity Subject RIV: CC - Organic Chemistry Impact factor: 3.065, year: 2014

  6. NaBH4/C: A Convenient System for Reductive Amination of Aldehydes

    Directory of Open Access Journals (Sweden)

    Sajjad Taie Hasanloie

    2014-03-01

    Full Text Available In this context, NaBH4 in the presence of activated charcoal has been used for thereductive aminationofa varietyof aldehydes withanilines. The reductive amination reactions have been performed within 60-100 min in THFunder reflux conditionsin high to excellent yields of products (85-90%.

  7. Size-Selective Oxidation of Aldehydes with Zeolite Encapsulated Gold Nanoparticles

    DEFF Research Database (Denmark)

    Højholt, Karen Thrane; Laursen, Anders Bo; Kegnæs, Søren;

    2011-01-01

    Here, we report a synthesis and catalytic study of hybrid materials comprised of 1–3 nm sinter-stable Au nanoparticles in MFI-type zeolites. An optional post-treatment in aqua regia effectively remove Au from the external surfaces. The size-selective aerobic aldehyde oxidation verifies that the...

  8. Supported Rh-phosphine complex catalysts for continuous gas-phase decarbonylation of aldehydes

    DEFF Research Database (Denmark)

    Malcho, Phillip; Garcia-Suarez, Eduardo J.; Mentzel, Uffe Vie; Engelbrekt, Christian; Riisager, Anders

    2014-01-01

    Heterogeneous silica supported rhodium-phosphine complex catalysts are employed for the first time in the catalytic decarbonylation of aldehydes in continuous gas-phase. The reaction protocol is exemplified for the decarbonylation of p-tolualdehyde to toluene and further extended to other aromatic...

  9. A General and Convenient Method for the Rhodium-Catalyzed Decarbonylation of Aldehydes

    DEFF Research Database (Denmark)

    Kreis, Michael; Palmelund, Anders; Bunch, Lennart; Madsen, Robert

    2006-01-01

    A practical protocol for the decarbonylation of a wide range of aldehydes has been developed by using commercially available RhCl3x3H2O and dppp in a diglyme solution. This method gives rise to decarbonylated products in good to high yield and is particularly useful because of its experimental si...

  10. APPLICATION OF MULTISPECTRAL TECHNIQUES TO THE PRECISE IDENTIFICATION OF ALDEHYDES IN THE ENVIRONMENT

    Science.gov (United States)

    By using gas chromatography coupled with low- and high-resolution electron impact mass spectrometry, low- and high-resolution chemical ionization mass spectrometry, and Fourier transform infrared spectroscopy, eight straight-chain aldehydes were identified in a water sample taken...

  11. Cu(I)-NHC-catalyzed silylation of allenes: diastereoselective three-component coupling with aldehydes.

    Science.gov (United States)

    Rae, James; Hu, Ya Chu; Procter, David J

    2014-10-01

    Copper-catalyzed silylation of aryl allenes using a silylborane reagent affords vinyl silane building blocks with high efficiency. The use of a seven-membered NHC ligand proved crucial for high regioselectivity. The catalytically generated allylcoppper intermediates were intercepted by aldehydes in a diastereoselective three-component coupling to furnish homoallylic alcohols. PMID:25146221

  12. Structure–anticancer activity relationships among 4-azolidinone-3-carboxylic acids derivatives

    Directory of Open Access Journals (Sweden)

    Lesyk R. B.

    2010-04-01

    Full Text Available The aim of present research was investigation of anticancer activity of 4-azolidinone-3-carboxylic acids derivatives, and studies of structure–activity relationships (SAR aspects. Methods. Organic synthesis; spectral methods; anticancer screening was performed according to the US NCI protocol (Developmental Therapeutic Program. Results. The data of new 4-thiazolidinone-3-alkanecarboxylic acids derivatives in vitro anticancer activity were described. The most active compounds which belong to 5-arylidene-2,4- thia(imidazolidinone-3-alkanecarboxylic acids; 5-aryl(heterylidenerhodanine-3-succinic acids derivatives were selected. Determination of some SAR aspects which allowed to determine directions in lead- compounds structure optimization, as well as desirable molecular fragments for design of potential anticancer agents based on 4-azolidinone scaffold were performed. 5-Arylidenehydantoin-3-acetic acids amides were identified as a new class of significant selective antileukemic agents. Possible pharmacophore scaffold of 5-ylidenerhodanine-3-succinic acids derivatives was suggested. Conclusions. The series of active compounds with high anticancer activity and/or selectivity levels were selected. Some SAR aspects were determined and structure design directions were proposed.

  13. The antimicrobial effects and metabolomic footprinting of carboxyl-capped bismuth nanoparticles against Helicobacter pylori.

    Science.gov (United States)

    Nazari, P; Dowlatabadi-Bazaz, R; Mofid, M R; Pourmand, M R; Daryani, N E; Faramarzi, M A; Sepehrizadeh, Z; Shahverdi, A R

    2014-01-01

    Organic salts of bismuth are currently used as antimicrobial agents against Helicobacter pylori. This study evaluated the antibacterial effect of elemental bismuth nanoparticles (Bi NPs) using a serial agar dilution method for the first time against different clinical isolates and a standard strain of H. pylori. The Bi NPs were biologically prepared and purified by a recently described method and subjected to further characterization by infrared spectroscopy and anti-H. pylori evaluation. Infrared spectroscopy results showed the presence of carboxyl functional groups on the surface of biogenic Bi NPs. These biogenic nanoparticles showed good antibacterial activity against all tested H. pylori strains. The resulting MICs varied between 60 and 100 μg/ml for clinical isolates of H. pylori and H. pylori (ATCC 26695). The antibacterial effect of bismuth ions was also tested against all test strains. The antimicrobial effect of Bi ions was lower than antimicrobial effect of bismuth in the form of elemental NPs. The effect of Bi NPs on metabolomic footprinting of H. pylori was further evaluated by (1)H NMR spectroscopy. Exposure of H. pylori to an inhibitory concentration of Bi NPs (100 μg/ml) led to release of some metabolites such as acetate, formic acid, glutamate, valine, glycine, and uracil from bacteria into their supernatant. These findings confirm that these nanoparticles interfere with Krebs cycle, nucleotide, and amino acid metabolism and shows anti-H. pylori activity. PMID:24104691

  14. Synthesis, Crystal and Molecular Structure Studies and DFT Calculations of Phenyl Quinoline-2-Carboxylate and 2-Methoxyphenyl Quinoline-2-Carboxylate; Two New Quinoline-2 Carboxylic Derivatives

    Directory of Open Access Journals (Sweden)

    Edakot Fazal

    2015-02-01

    Full Text Available The crystal and molecular structures of the title compounds, phenyl quinoline-2-carboxylate and 2-methoxyphenyl quinoline-2-carboxylate, two new derivatives of quinolone-2-carboxylic acid, are reported and confirmed by single crystal X-ray diffraction and spectroscopic data. Compound (I, C16H11NO2, crystallizes in the monoclinic space group P21/c, with 8 molecules in the unit cell. The unit cell parameters are a = 14.7910(3 Å; b = 5.76446(12 Å; c = 28.4012(6 Å; β = 99.043(2°; V = 2391.45(9 Å3. Compound (II, C17H13NO5, crystallizes in the monoclinic space group P21/n with 4 molecules in the unit cell. The unit cell parameters are a = 9.6095(3 Å; b = 10.8040(3 Å; c = 13.2427(4 Å; β = 102.012(3°; V = 1344.76(7 Å3. Density functional theory (DFT geometry optimized molecular orbital calculations were performed and frontier molecular orbitals of each compound are displayed. Correlation between the calculated molecular orbital energies (eV for the surfaces of the frontier molecular orbitals to the electronic excitation transitions from the absorption spectra of each compound has been proposed. Additionally, similar correlations observed among six closely related compounds examining small structural differences to their frontier molecular orbital surfaces and from their DFT molecular orbital energies, provide further support for the suggested assignments of the title compounds.

  15. Aldehyde Dehydrogenase Type 2 Activation by Adenosine and Histamine Inhibits Ischemic Norepinephrine Release in Cardiac Sympathetic Neurons: Mediation by Protein Kinase Cε

    OpenAIRE

    Robador, Pablo A.; Seyedi, Nahid; Chan, Noel Yan-Ki; Koda, Kenichiro; Levi, Roberto

    2012-01-01

    During myocardial ischemia/reperfusion, lipid peroxidation leads to the formation of toxic aldehydes that contribute to ischemic dysfunction. Mitochondrial aldehyde dehydrogenase type 2 (ALDH2) alleviates ischemic heart damage and reperfusion arrhythmias via aldehyde detoxification. Because excessive norepinephrine release in the heart is a pivotal arrhythmogenic mechanism, we hypothesized that neuronal ALDH2 activation might diminish ischemic norepinephrine release. Incubation of cardiac sym...

  16. Synthesis and properties of starch-g-poly(maleic anhydride-co-vinyl acetate

    Directory of Open Access Journals (Sweden)

    2010-01-01

    Full Text Available Starch-g-poly(maleic anhydride-co-vinyl acetate (SMV was synthesized via the esterification reaction of starch with the copolymer of maleic anhydride and vinyl acetate. The carboxylic unit percentage (CUP of SMV was tailored with reaction conditions, and it ranged from 29.8 to 46.9%. The structure and the morphology of the copolymers were characterized with Fourier Transform Infrared spectroscopy and X-ray diffraction analysis. It was found that SMV could form complex with some metal cations such as Ca2+, Pb2+ and Hg2+ or cationic polyelectrolyte chitosan, and precipitate from the solution. The weight of precipitation increases with an increase of the CUP of SMV. In addition, a physically cross-linked hydrogel of SMV/poly(vinyl alcohol (PVA was obtained by freeze/thaw technique. Scanning electron microscopy exhibited the hydrogel was uniform. The gel exhibited pH-responsive re-swelling. The maximum swelling-ratio values of SMV/PVA (9:1, wt/wt gel were 3.29 and 5.34 in HCl (pH 1.0 and phosphate-buffer saline (PBS (pH 12 respectively.

  17. Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation

    Directory of Open Access Journals (Sweden)

    P. O. Wennberg

    2010-04-01

    Full Text Available Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene, the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA via methacrolein (a C4-unsaturated aldehyde under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232 is insignificant, even under high-NO2 conditions, as PAN (peroxy acyl nitrate, RC(OOONO2 formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios, the SOA yields from isoprene high-NOxphotooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

  18. Role of aldehyde chemistry and NOx concentrations in secondary organic aerosol formation

    Directory of Open Access Journals (Sweden)

    P. O. Wennberg

    2010-08-01

    Full Text Available Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene, the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA via methacrolein (a C4-unsaturated aldehyde under urban high-NOx conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN as the important intermediate to isoprene and methacrolein SOA in this NOx regime. Here we show that as a result of this chemistry, NO2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NOx effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232 is insignificant, even under high-NO2 conditions, as PAN (peroxy acyl nitrate, RC(OOONO2 formation is structurally unfavorable. At atmospherically relevant NO2/NO ratios (3–8, the SOA yields from isoprene high-NOx photooxidation are 3 times greater than previously measured at lower NO2/NO ratios. At sufficiently high NO2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO2 can exceed that from RO2+HO2 reactions under the same inorganic seed conditions, making RO2+NO2 an important channel for SOA formation.

  19. Cytochrome P450BM-3 reduces aldehydes to alcohols through a direct hydride transfer

    Energy Technology Data Exchange (ETDEWEB)

    Kaspera, Ruediger; Sahele, Tariku; Lakatos, Kyle [Department of Medicinal Chemistry, University of Washington, Box 357610, Seattle, WA 98195-7610 (United States); Totah, Rheem A., E-mail: rtotah@u.washington.edu [Department of Medicinal Chemistry, University of Washington, Box 357610, Seattle, WA 98195-7610 (United States)

    2012-02-17

    Highlights: Black-Right-Pointing-Pointer Cytochrome P450BM-3 reduced aldehydes to alcohols efficiently (k{sub cat} {approx} 25 min{sup -1}). Black-Right-Pointing-Pointer Reduction is a direct hydride transfer from R-NADP{sup 2}H to the carbonyl moiety. Black-Right-Pointing-Pointer P450 domain variants enhance reduction through potential allosteric/redox interactions. Black-Right-Pointing-Pointer Novel reaction will have implications for metabolism of xenobiotics. -- Abstract: Cytochrome P450BM-3 catalyzed the reduction of lipophilic aldehydes to alcohols efficiently. A k{sub cat} of {approx}25 min{sup -1} was obtained for the reduction of methoxy benzaldehyde with wild type P450BM-3 protein which was higher than in the isolated reductase domain (BMR) alone and increased in specific P450-domain variants. The reduction was caused by a direct hydride transfer from preferentially R-NADP{sup 2}H to the carbonyl moiety of the substrate. Weak substrate-P450-binding of the aldehyde, turnover with the reductase domain alone, a deuterium incorporation in the product from NADP{sup 2}H but not D{sub 2}O, and no inhibition by imidazole suggests the reductase domain of P450BM-3 as the potential catalytic site. However, increased aldehyde reduction by P450 domain variants (P450BM-3 F87A T268A) may involve allosteric or redox mechanistic interactions between heme and reductase domains. This is a novel reduction of aldehydes by P450BM-3 involving a direct hydride transfer and could have implications for the metabolism of endogenous substrates or xenobiotics.

  20. Light dependence of carboxylation capacity for C3 photosynthesis models

    Science.gov (United States)

    Photosynthesis at high light is often modelled by assuming limitation by the maximum capacity of Rubisco carboxylation at low carbon dioxide concentrations, by electron transport capacity at higher concentrations, and sometimes by triose-phosphate utilization rate at the highest concentrations. Pho...

  1. Conformation of some carboxylic acids and their derivatives

    NARCIS (Netherlands)

    Kanters, J.A.; Kroon, Jan; Peerdeman, A.F.; Schoone, J.C.

    1967-01-01

    The conformation in the crystalline state of some aliphatic carboxylic acids and their derivatives has been analysed. This analysis, based upon the results of structure determinations by means of X-ray diffraction, seems to support the concept that the conformation of a molecule is governed chiefly

  2. Acidity of carboxylic acids: a rebuttal and redefinition

    Czech Academy of Sciences Publication Activity Database

    Exner, Otto; Čársky, Petr

    2001-01-01

    Roč. 123, č. 39 (2001), s. 9564-9570. ISSN 0002-7863 R&D Projects: GA ČR GA203/99/1454 Institutional research plan: CEZ:AV0Z4055905 Keywords : carboxylic acids Subject RIV: CC - Organic Chemistry Impact factor: 6.079, year: 2001

  3. Organometallic carboxylate resists for extreme ultraviolet with high sensitivity

    Science.gov (United States)

    Passarelli, James; Murphy, Michael; Re, Ryan Del; Sortland, Miriam; Hotalen, Jodi; Dousharm, Levi; Fallica, Roberto; Ekinci, Yasin; Neisser, Mark; Freedman, Daniel A.; Brainard, Robert L.

    2015-10-01

    We have developed organometallic carboxylate compounds [RnM)] capable of acting as negative-tone extreme ultraviolet (EUV) resists. The most sensitive of these resists contain antimony, three R-groups and two carboxylate groups, and carboxylate groups with polymerizable olefins (e.g., acrylate, methacrylate, or styrenecarboxylate). Evidence suggests that high sensitivity is achieved through the polymerization of olefins in the exposed region. We have performed a systematic sensitivity study of the molecules of the type RnM) where we have studied seven R groups, four main group metals (M), and three polymerizable carboxylate groups (O2CR‧). The sensitivity of these resists was evaluated using Emax or dose to maximum resist thickness after exposure and development. We found that the greatest predictor of sensitivity of the RnSb) resists is their level of polymerizable olefins. We mathematically define the polymerizable olefin loading (POL) as the ratio of the number of olefins versus the number of nonhydrogen atoms. Linear and log plots of Emax versus POL for a variety of molecules of the type R3Sb) lend insight into the behavior of these resists.

  4. Synthesis of (2R,3aR,8aR)-6-Chloro-3a-hydroxy-1,2,3,3a,8,8a- hexahydropyrrolo[2,3-b]indole-2-carboxylic Acid Methyl Ester by Reductive Cyclization

    Institute of Scientific and Technical Information of China (English)

    HONG,Wen-Xu(洪文旭); YAO,Zhu-Jun(姚祝军)

    2004-01-01

    A synthesis of(2R,3aR,8aR)-6-chloro-3a-hydroxy-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indole-2-carboxylic acid methyl ester(1)was achieved.An aldol reaction with Garner aldehyde,a hydroxyl introduction by Davis reagent,and a reductive intramolecular ring-closure reaction were served as the key steps.This piece of work provides a new way to synthesize the analogues of hexahydropyrrolo[2,3-b]indole,starting from readily available chemical substrates and inexpensive reagents.

  5. Development and validation of a reversed-phase liquid chromatography method for the quantitative determination of carboxylic acids in industrial reaction mixtures.

    Science.gov (United States)

    Destandau, E; Vial, J; Jardya, A; Henniona, M C; Bonnet, D; Lancelin, P

    2005-09-23

    Usually analysis of low molecular-mass carboxylic acids was performed by anion-exchange or ion-exclusion chromatographic methods. Reversed-phase liquid chromatography (RPLC) was evaluated in this work as an alternative method for the analysis of low molecular-mass aliphatic mono- and di-carboxylic acids (formic, acetic, propionic, butyric, valeric, caproic, succinic, glutaric and adipic) in aqueous media. The separation of the nine organic acids was optimised in 21 min on a high-density C18 column with an elution gradient made up of HClO4 aqueous solution 10(-3) mol L(-1) and acetonitrile. For the quantitation, external standard and standard addition methods were compared. Both methods gave similar results, so the most convenient method, external standard, was chosen for acids quantitation. Then the method had been validated and applied to the semi-quantitative analysis of formic and acetic acids and to the quantitative analysis of the others compounds in industrial reaction mixtures with concentrations ranging from 20 to 570 ppm. PMID:16130732

  6. Acetic acid extraction from aqueous solutions using fatty acids

    NARCIS (Netherlands)

    IJmker, H.M.; Gramblicka, M.; Kersten, S.R.A.; Ham, van der A.G.J.; Schuur, B.

    2014-01-01

    A major challenge for production of acetic acid via bio-based routes is cost-effective concentration and purification of the acetic acid from the aqueous solutions, for which liquid–liquid extraction is a possible method. A main challenge in extraction of acetic acid from dilute aqueous solutions is

  7. Microbial acetate oxidation in horizontal rotating tubular bioreactor

    Indian Academy of Sciences (India)

    A Slavica; B Šantek; S Novak; V Marić

    2004-06-01

    The aim of this work was to investigate the possibility of conducting a continuous aerobic bioprocess in a horizontal rotating tubular bioreactor (HRTB). Aerobic oxidation of acetate by the action of a mixed microbial culture was chosen as a model process. The microbial culture was not only grown in a suspension but also in the form of a biofilm on the interior surface of HRTB. Efficiency of the bioprocess was monitored by determination of the acetate concentration and chemical oxygen demand (COD). While acetate inlet concentration and feeding rate influenced efficiency of acetate oxidation, the bioreactor rotation speed did not influence the bioprocess dynamics significantly. Gradients of acetate concentration and pH along HRTB were more pronounced at lower feeding rates. Volumetric load of acetate was proved to be the most significant parameter. High volumetric loads (above 2 g acetate l–1 h–1) gave poor acetate oxidation efficiency (only 17 to 50%). When the volumetric load was in the range of 0.60–1.75 g acetate l–1 h–1, acetate oxidation efficiency was 50–75%. At lower volumetric loads (0.14–0.58 g acetate l–1 h–1), complete acetate consumption was achieved. On the basis of the obtained results, it can be concluded that HRTB is suitable for conducting aerobic continuous bioprocesses.

  8. Addressing Cellulose Acetate Microfilm from a British Library perspective

    Directory of Open Access Journals (Sweden)

    Helen Shenton

    2005-08-01

    Full Text Available This paper is about cellulose acetate microfilm from the British Library perspective. It traces how acetate microfilm became an issue for the British Library and describes cellulose acetate deterioration. This is followed by details of what has already been done about the situation and what action is planned for the future.

  9. Fermentation characteristics of Fusarium oxysporum grown on acetate

    DEFF Research Database (Denmark)

    Panagiotou, Gianni; Pachidou, Fotini; Petroutsos, Dimitris;

    2008-01-01

    In this study, the growth characteristics of Fusarium oxysporum were evaluated in minimal medium using acetate or different mixtures of acetate and glucose as carbon source. The minimum inhibitory concentration (MIC) of acetic acid that F oxysporum cells could tolerate was 0.8% w/v while glucose...

  10. PHOTOCOPOLYMERIZATION OF MALEIC ANHYDRIDE AND VINYL ACETATE

    Institute of Scientific and Technical Information of China (English)

    LI Xiaofang; LI Shanjun; QIN Anwei; YU Tongyin

    1990-01-01

    The charge-transfer complex of maleic anhydride and vinyl acetate was copolymerized under UV light. The chain composition and structure of the copolymer were analyzed with conductometry and NMR, and the chain sequence was determined as alternating. The copolymerization rates at different feed ratios, temperatures and in different solvents were investigated, giving evidence to the very active involvement of the CT complexes in the copolymerization. Terpolymerization with acrylonitrile also showed that the complex mechanism was a proper one for this system.

  11. Acet­oxy-γ-valerolactone

    OpenAIRE

    Tristram, Cameron; Graeme J. Gainsford; Hinkley, Simon

    2013-01-01

    Levulinyl cellulose esters have been produced as an effective renewable binder for architectural coatings. The title compound, C7H10O4 (systematic name: 2-methyl-5-oxo­tetra­hydro­furan-2-yl acetate), assigned as the esterifying species, was isolated and crystallized to confirm the structure. In the crystal, the mol­ecules pack in layers parallel to (102) utilizing weak C—H⋯O inter­actions.

  12. Carboxyl-Functionalized Ionic Liquid Assisted Preparation of Flexible, Transparent, and Luminescent Chitosan Films as Vapor Luminescent Sensor.

    Science.gov (United States)

    Yang, Daqing; Wang, Yige; He, Liang; Li, Huanrong

    2016-08-01

    Herein we present a novel method to synthesize flexible self-standing films consisting of europium(III) complexes in nanoclay and chitosan, which are transparent and luminescent. Preparation takes place under aqueous conditions assisted by a carboxyl-functionalized ionic liquid (IL). The latter is used not only as a replacement for acetic acid to dissolve chitosan but, surprisingly, also to enhance the luminescence efficiency of the final films. A brighter luminescence is observed for the films prepared assisted with the ionic liquids compared to those by using acetic acid. The reason is that the ionic liquid used to dissolve chitosan can decrease proton strength on embedded platelets primarily through ion-exchange process and thus can increase the coordination number of europium(III) complexes. Exposure of the films to Et3N vapors can cause a further remarkable luminescence enhancement, while significant luminescence quenching occurred upon exposure to HCl vapors. The films are promising for applications in areas such as optoelectronics and vapor-sensitive luminescent sensors. PMID:27424528

  13. The addition of norethindrone acetate to leuprolide acetate for ovarian suppression has no adverse effect on ovarian stimulation

    OpenAIRE

    Ditkoff, Edward C.; Prosser, Robert; Zimmermann, Ralf C; Lindheim, Steven; Sauer, Mark V.

    1997-01-01

    Purpose: Our goal was to determine if the addition of norethindrone acetate (NETA) to leuprolide acetate (LA) has an adverse effect on controlled ovarian stimulation (COH) during in vitro fertilization (IVF).

  14. Amino acetate functionalized Schiff base organotin(IV) complexes as anticancer drugs: synthesis, structural characterization, and in vitro cytotoxicity studies.

    Science.gov (United States)

    Baul, Tushar S Basu; Basu, Smita; de Vos, Dick; Linden, Anthony

    2009-10-01

    Potassium 2-{[(2Z)-(3-hydroxy-1-methyl-2-butenylidene)]amino}-4-methyl-pentanoate (L(1)HK) and potassium 2-{[(E)-1-(2-hydroxyphenyl)alkylidene]amino}-4-methyl-pentanoates (L(2)HK-L(3)HK) underwent reactions with Ph(n)SnCl(4-n) (n = 2 and 3) to give the amino acetate functionalized Schiff base organotin(IV) complexes [Ph(3)SnLH](n)(1-3) and [Ph(2)SnL] (4), respectively. These complexes have been characterized by (1)H, (13)C, (119)Sn NMR, IR spectroscopic techniques in combination with elemental analyses. The crystal structures of 1 and 3 were determined. The crystal structures reveal that the complexes exist as polymeric chains in which the L-bridged Sn-atoms adopt a trans-R(3)SnO(2) trigonal bipyramidal configuration with the Ph groups in the equatorial positions and the axial locations occupied by a carboxylate oxygen atom from one carboxylate ligand and the alcoholic or phenolic oxygen atom of the next carboxylate ligand in the chain. The carboxylate ligands coordinate in the zwitterionic form with the alcoholic/phenolic proton moved to the nearby nitrogen atom. The solution structures were predicted by (119)Sn NMR spectroscopy. When these organotin(IV) complexes were tested against A498, EVSA-T, H226, IGROV, M19 MEL, MCF7 and WIDR human tumor cell lines, the average ID(50) values obtained were 55, 80 and 35 ng/ml for triphenyltin(IV) compounds 1-3, respectively. The most cytotoxic triphenyltin(IV) compound in the present report (3) with an average ID(50) value of around 35 ng/ml is found to be more cytotoxic for all the cell lines studied than doxorubicin, cisplatin, 5-fluorouracil and etoposide. PMID:18941713

  15. 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.

  16. Isolation of liver aldehyde oxidase containing fractions from different animals and determination of kinetic parameters for benzaldehyde

    Directory of Open Access Journals (Sweden)

    Kadam R

    2008-01-01

    Full Text Available Aldehyde oxidase activity containing fractions from rabbit, guinea pig, rat and mouse livers were obtained by heat treatment and ammonium sulfate precipitation. Aldehyde oxidase activity was observed in rabbit and guinea pig livers, while aldehyde oxidase activity was absent in rat and mouse liver fractions. Enzyme kinetic parameters, K m and V max , were determined for the oxidation of benzaldehyde to benzoic acid by rabbit and guinea pig liver fractions, by spectrophotometric method, with potassium ferricyanide as the electron acceptor. The K m values obtained for both animal liver fractions were in the range of 10.3-19.1 µM.

  17. 40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated carboxylic acid alkali... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under...

  18. 40 CFR 721.10142 - Oxabicycloalkane carboxylic acid alkanediyl ester (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Oxabicycloalkane carboxylic acid... New Uses for Specific Chemical Substances § 721.10142 Oxabicycloalkane carboxylic acid alkanediyl... substance identified generically as oxabicycloalkane carboxylic acid alkanediyl ester (PMN P-06-199)...

  19. The synthesis, structure and properties of N-acetylated derivatives of ethyl 3-amino-1H-pyrazole-4-carboxylate.

    Science.gov (United States)

    Kusakiewicz-Dawid, Anna; Masiukiewicz, Elzbieta; Rzeszotarska, Barbara; Dybała, Izabela; Kozioł, Anna Eugenia; Broda, Małgorzata Anna

    2007-05-01

    Ethyl 3-amino-1H-pyrazole-4-carboxylate (1) was yielded through total synthesis and reacted with acetic anhydride to give the acetylated products 2-6. Compounds 1-6 were studied with HPLC, X-ray, FT-IR, (1)H-NMR, (13)C-NMR and MS. Acetylation was carried out in solvents of various polarity, namely; chloroform; dioxane; DMF; acetic anhydride, at room temperature and at boiling points; and in the presence and absence of DMAP. The acetylated products are mainly nitrogen atoms in the ring. The position of the ring proton in the solution was based on NOESY; multinuclear HMBC, HSQC spectra and calculations. For equivalent amounts (1-1.5 mol) of acetic anhydride at room temperature two products of monoacetylation are produced in the ring: 2 and 3, ca. 2 : 1 and at the same time only small amount of the third product of monoacetylated, 5 in DMF, as well the product diacetylated, 4. The greatest amount of the product 4 is produced during the reaction with chloroform. However, in this solvent and in dioxane no product 5 is produced. Compound 2 is, largely, formed in dimethylformamide, in the presence DMAP, 0.2 eq. In the presence of this catalytic base, for the first hour, there is a mixture 2 and 3 to the ratio ca. 95 : 5. With 8 eq of Ac(2)O at reflux, after another hour, the compounds 3, 4 and 6 appear about equal amounts. After a longer time, the compound, which appears most in this mixture is triacetylated derivative 6. The structural and spectroscopic characteristics of compounds 1-6 have been given and the methods for their preparation have been provided. PMID:17473461

  20. Simultaneous Determination and Pharmacokinetic Study of Protocatechuic Aldehyde and Its Major Active Metabolite Protocatechuic Acid in Rat Plasma by Liquid Chromatography-Tandem Mass Spectrometry.

    Science.gov (United States)

    Wang, Xiangyang; Yan, Kaijing; Ma, Xiaohui; Li, Wei; Chu, Yang; Guo, Jiahua; Li, Shuming; Zhou, Shuiping; Zhu, Yonghong; Liu, Changxiao

    2016-05-01

    A very simple and selective high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-MS-MS) method was developed for simultaneous determination and pharmacokinetic study of protocatechuic aldehyde (PAL) and its active metabolite protocatechuic acid (PCA). The method involves a simple liquid-liquid extraction with ethyl acetate. The separation was performed on a Hypersil GOLD C18column (2.1 × 150 mm, 3.0 µm; particle, Thermo, USA) with isocratic elution using a mobile phase consisted of methanol and water (containing 0.1% formic acid) at a flow rate of 0.2 mL/min. The detection of target compounds was done by using low-energy collision dissociation tandem mass spectrometry (CID-MS-MS) using the selective reaction monitoring scan mode. The method was linear for all analytes over the investigated range for all correlation coefficients greater than 0.9950. The lower limits of quantification were 2.0 ng/mL for PAL and PCA. The intra- and interday precisions (relative standard deviation, RSD %) were <6.84 and 5.54%, and the accuracy (relative error, RE %) was between -2.85 and 0.74% (n= 6). The developed method was applied to study the pharmacokinetics of PAL and its major active metabolite PCA in rat plasma after oral and intravenous administration of PAL. PMID:26969682

  1. [Degradation of oxytetracycline with ozonation in acetic acid solvent].

    Science.gov (United States)

    Li, Shi-Yin; Li, Xiao-Rong; Zhu, Yi-Ping; Zhu, Jiang-Peng; Wang, Guo-Xiang

    2012-12-01

    Use acetic acid as the media of ozone degradation of oxytetracycline (OTC), and effects of the initial dosing ratio of ozone/OTC, ozone flow, free radical scavenger, metal ions on the removal rate of OTC were investigated respectively. The results showed that acetic acid had a high ozone stability and solubility. OTC had a high removal rate and degradation rate in acetic acid solution. With the increase of OTC dosage, the removal rate of OTC decreased in acetic acid. Removal rate of OTC was increased distinctly when ozone flow increased properly. It was also observed that free radical scavenger had a significantly negative effect on OTC ozonation degradation in acetic acid. Furthermore the main reactions of OTC ozone oxidation were direct oxidation and indirect oxidation in acetic acid. When Fe3+ and Co2+ were existent in acetic acid, the degradation of OTC was inhibited significantly. PMID:23379161

  2. Crystal structures of the potassium and rubidium salts of (3,5-di-chloro-phen-oxy)acetic acid: two isotypic coordination polymers.

    Science.gov (United States)

    Smith, Graham

    2015-10-01

    The two-dimensional coordination polymeric structures of the hydrated potassium and rubidium salts of (3,5-di-chloro-phen-oxy)acetic acid (3,5-D), namely, poly[μ-aqua-bis-[μ3-2-(3,5-di-chloro-phen-oxy)acetato]-dipotassium], [K2(C8H5Cl2O3)2(H2O)] n , and poly[μ-aqua-bis-[μ3-2-(3,5-di-chloro-phen-oxy)acetato]-dirubidium], [Rb2(C8H5Cl2O3)2(H2O)] n , respectively, have been determined and are described. The two compounds are isotypic and the polymeric structure is based on centrosymmetric dinuclear bridged complex units. The irregular six-coordination about the alkali cations comprises a bridging water mol-ecule lying on a twofold rotation axis, the phen-oxy O-atom donor and a triple bridging carboxyl-ate O atom of the oxo-acetate side chain of the 3,5-D ligand, and the second carb-oxy-ate O-atom donor also bridging. The K-O and Rb-O bond-length ranges are 2.7238 (15)-2.9459 (14) and 2.832 (2)-3.050 (2) Å, respectively, and the K⋯K and Rb⋯Rb separations in the dinuclear units are 4.0214 (7) and 4.1289 (6) Å, respectively. Within the layers which lie parallel to (100), the coordinating water mol-ecule forms an O-H⋯O hydrogen bond to the single bridging carboxyl-ate O atom. PMID:26594400

  3. Acetic acid removal from corn stover hydrolysate using ethyl acetate and the impact on Saccharomyces cerevisiae bioethanol fermentation.

    Science.gov (United States)

    Aghazadeh, Mahdieh; Ladisch, Michael R; Engelberth, Abigail S

    2016-07-01

    Acetic acid is introduced into cellulose conversion processes as a consequence of composition of lignocellulose feedstocks, causing significant inhibition of adapted, genetically modified and wild-type S. cerevisiae in bioethanol fermentation. While adaptation or modification of yeast may reduce inhibition, the most effective approach is to remove the acetic acid prior to fermentation. This work addresses liquid-liquid extraction of acetic acid from biomass hydrolysate through a pathway that mitigates acetic acid inhibition while avoiding the negative effects of the extractant, which itself may exhibit inhibition. Candidate solvents were selected using simulation results from Aspen Plus™, based on their ability to extract acetic acid which was confirmed by experimentation. All solvents showed varying degrees of toxicity toward yeast, but the relative volatility of ethyl acetate enabled its use as simple vacuum evaporation could reduce small concentrations of aqueous ethyl acetate to minimally inhibitory levels. The toxicity threshold of ethyl acetate, in the presence of acetic acid, was found to be 10 g L(-1) . The fermentation was enhanced by extracting 90% of the acetic acid using ethyl acetate, followed by vacuum evaporation to remove 88% removal of residual ethyl acetate along with 10% of the broth. NRRL Y-1546 yeast was used to demonstrate a 13% increase in concentration, 14% in ethanol specific production rate, and 11% ethanol yield. This study demonstrated that extraction of acetic acid with ethyl acetate followed by evaporative removal of ethyl acetate from the raffinate phase has potential to significantly enhance ethanol fermentation in a corn stover bioethanol facility. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:929-937, 2016. PMID:27090191

  4. Adaptation and tolerance of bacteria against acetic acid.

    Science.gov (United States)

    Trček, Janja; Mira, Nuno Pereira; Jarboe, Laura R

    2015-08-01

    Acetic acid is a weak organic acid exerting a toxic effect to most microorganisms at concentrations as low as 0.5 wt%. This toxic effect results mostly from acetic acid dissociation inside microbial cells, causing a decrease of intracellular pH and metabolic disturbance by the anion, among other deleterious effects. These microbial inhibition mechanisms enable acetic acid to be used as a preservative, although its usefulness is limited by the emergence of highly tolerant spoilage strains. Several biotechnological processes are also inhibited by the accumulation of acetic acid in the growth medium including production of bioethanol from lignocellulosics, wine making, and microbe-based production of acetic acid itself. To design better preservation strategies based on acetic acid and to improve the robustness of industrial biotechnological processes limited by this acid's toxicity, it is essential to deepen the understanding of the underlying toxicity mechanisms. In this sense, adaptive responses that improve tolerance to acetic acid have been well studied in Escherichia coli and Saccharomyces cerevisiae. Strains highly tolerant to acetic acid, either isolated from natural environments or specifically engineered for this effect, represent a unique reservoir of information that could increase our understanding of acetic acid tolerance and contribute to the design of additional tolerance mechanisms. In this article, the mechanisms underlying the acetic acid tolerance exhibited by several bacterial strains are reviewed, with emphasis on the knowledge gathered in acetic acid bacteria and E. coli. A comparison of how these bacterial adaptive responses to acetic acid stress fit to those described in the yeast Saccharomyces cerevisiae is also performed. A systematic comparison of the similarities and dissimilarities of the ways by which different microbial systems surpass the deleterious effects of acetic acid toxicity has not been performed so far, although such exchange

  5. Selective Production of Aromatic Aldehydes from Heavy Fraction of Bio-oil via Catalytic Oxidation

    International Nuclear Information System (INIS)

    High value-added aromatic aldehydes (e. g. vanillin and syringaldehyde) were produced from heavy fraction of bio-oil (HFBO) via catalytic oxidation. The concept is based on the use of metalloporphyin as catalyst and hydrogen peroxide (H2O2) as oxidant under alkaline condition. The biomimetic catalyst cobalt(II)-sulfonated tetraphenylporphyrin (Co(TPPS4)) was prepared and characterized. It exhibited relative high activity in the catalytic oxidation of HFBO. 4.57 wt % vanillin and 1.58 wt % syringaldehyde were obtained from catalytic oxidation of HFBO, compared to 2.6 wt % vanillin and 0.86 wt % syringaldehyde without Co(TPPS4). Moreover, a possible mechanism of HFBO oxidation using Co(TPPS4)/H2O2 was proposed by the research of model compounds. The results showed that this is a promising and environmentally friendly method for production of aromatic aldehydes from HFBO under Co(TPPS4)/H2O2 system

  6. Biomass Vanillin-Derived Polymeric Microspheres Containing Functional Aldehyde Groups: Preparation, Characterization, and Application as Adsorbent.

    Science.gov (United States)

    Zhang, Huanyu; Yong, Xueyong; Zhou, Jinyong; Deng, Jianping; Wu, Youping

    2016-02-01

    The contribution reports the first polymeric microspheres derived from a biomass, vanillin. It reacted with methacryloyl chloride, providing monomer vanillin methacrylate (VMA), which underwent suspension polymerization in aqueous media and yielded microspheres in high yield (>90 wt %). By controlling the N2 bubbling mode and by optimizing the cosolvent for dissolving the solid monomer, the microspheres were endowed with surface pores, demonstrated by SEM images and mercury intrusion porosimetry measurement. Taking advantage of the reactive aldehyde groups, the microspheres further reacted with glycine, thereby leading to a novel type of Schiff-base chelating material. The functionalized microspheres demonstrated remarkable adsorption toward Cu(2+) (maximum, 135 mg/g) which was taken as representative for metal ions. The present study provides an unprecedented class of biobased polymeric microspheres showing large potentials as adsorbents in wastewater treatment. Also importantly, the reactive aldehyde groups may enable the microspheres to be used as novel materials for immobilizing biomacromolecules, e.g. enzymes. PMID:26752344

  7. Functionalization of carbon nanotube by carboxyl group under radial deformation

    Science.gov (United States)

    Lara, Ivi Valentini; Zanella, Ivana; Fagan, Solange Binotto

    2014-01-01

    The dependence of the structural and the electronic properties of functionalized (5, 5) single-walled carbon nanotubes (SWNT) were investigated through ab initio density functional simulations when the carboxyl group is bonded on the flatter or curved regions. Radial deformations result in diameter decrease of up to 20 per cent of the original size, which was the limit reduction that maintains the SWNT functionalized structure. Changes on the electronic structure were observed due to the symmetry break of the SWNT caused by both the carboxyl group and the C-C bond distortions resulted by the radial deformation. It is observed that the functionalization process is specially favored by the sp3 hybridization induced on the more curved region of the deformed SWNT.

  8. Enhance decarboxylation reaction of carboxylic acids in clay minerals

    International Nuclear Information System (INIS)

    Clay minerals are important constituents of the Earth's crust. These minerals catalyze reactions in several ways: by energy transfer processes, redox reactions, stabilization of intermediates and by Broensted or Lewis acidity behavior. Important set of organic reactions can be improved in the precedence of clay minerals. Besides the properties of clays to catalyze chemical reactions, it is possible to enhance some of its reactions by using ionizing radiation. The phenomenon of radiation-induced catalysis may be connected with ionizing process in the solid and with the trapped non-equilibrium charge carriers. In this paper we are reporting the decarboxylation reaction of carboxylic acids catalyzed by clay and by irradiation of the system acid-clay. We studied the behaviour of several carboxylic acids and analyzed them by gas chromatography, X-ray and infrared spectroscopy. The results showed that decarboxylation of the target compound is the dominating pathway. The reaction is enhanced by gamma radiation in several orders of magnitude. (author)

  9. 1-(5,5-Dimethoxypentyl-3-methylimidazolium-2-carboxylate

    Directory of Open Access Journals (Sweden)

    Olaf Walter

    2013-11-01

    Full Text Available The title compound, C12H20N2O4, represents one example of a zwitterionic imidazolium salt with a carboxylate group at the 2-position of the imidazolium ring. The dihedral angle between the heterocyclic ring and the carboxylate group is 31.3 (1°. The side chain linking the N atom of the ring and the methine C atom has a gauche–anti–anti conformation [torsion angles = −60.3 (2, −175.7 (2 and 178.7 (2°, respectively]. In the crystal, molecules are linked by short C—H...O hydrogen bonds involving the C—H groups in the aromatic ring to generate (001 sheets.

  10. Sensing of antipyretic carboxylates by simple chromogenic calix[4]pyrroles.

    Science.gov (United States)

    Nishiyabu, Ryuhei; Anzenbacher, Pavel

    2005-06-15

    We present a simple, two- or three-step method for the synthesis of chromogenic octamethylcalix[4]pyrrole-based (OMCP) sensors for anions. Electrophilic aromatic substitution allows for converting the pyrrole moieties of OMCP into a dye. The formation of a sensor-anion complex results in partial charge transfer and a dramatic change in color. The absorption (UV-vis) and NMR titration experiments show that the chromogenic OMCPs sense anions administered as aqueous solutions, even at high ionic strength ( approximately 0.1 M NaCl), while displaying selectivity for pyrophosphate and carboxylate anions. The experiments with polyurethane sensor films show a strong response for aqueous carboxylates, such as antipyretics naproxen approximately ibuprofen > salicylate, without being biased by bicarbonate or carboxy termini of blood plasma proteins. PMID:15941245

  11. Substrate specificity within a family of outer membrane carboxylate channels.

    Directory of Open Access Journals (Sweden)

    Elif Eren

    2012-01-01

    Full Text Available Many Gram-negative bacteria, including human pathogens such as Pseudomonas aeruginosa, do not have large-channel porins. This results in an outer membrane (OM that is highly impermeable to small polar molecules, making the bacteria intrinsically resistant towards many antibiotics. In such microorganisms, the majority of small molecules are taken up by members of the OprD outer membrane protein family. Here we show that OprD channels require a carboxyl group in the substrate for efficient transport, and based on this we have renamed the family Occ, for outer membrane carboxylate channels. We further show that Occ channels can be divided into two subfamilies, based on their very different substrate specificities. Our results rationalize how certain bacteria can efficiently take up a variety of substrates under nutrient-poor conditions without compromising membrane permeability. In addition, they explain how channel inactivation in response to antibiotics can cause resistance but does not lead to decreased fitness.

  12. Enhancing magnetoresistance in tetrathiafulvalene carboxylate modified iron oxide nanoparticle assemblies

    Science.gov (United States)

    Lv, Zhong-Peng; Luan, Zhong-Zhi; Cai, Pei-Yu; Wang, Tao; Li, Cheng-Hui; Wu, Di; Zuo, Jing-Lin; Sun, Shouheng

    2016-06-01

    We report a facile approach to stabilize Fe3O4 nanoparticles (NPs) by using tetrathiafulvalene carboxylate (TTF-COO-) and to control electron transport with an enhanced magnetoresistance (MR) effect in TTF-COO-Fe3O4 NP assemblies. This TTF-COO-coating is advantageous over other conventional organic coatings, making it possible to develop stable Fe3O4 NP arrays for sensitive spintronics applications.We report a facile approach to stabilize Fe3O4 nanoparticles (NPs) by using tetrathiafulvalene carboxylate (TTF-COO-) and to control electron transport with an enhanced magnetoresistance (MR) effect in TTF-COO-Fe3O4 NP assemblies. This TTF-COO-coating is advantageous over other conventional organic coatings, making it possible to develop stable Fe3O4 NP arrays for sensitive spintronics applications. Electronic supplementary information (ESI) available: Experimental details; supplementary figures and tables. See DOI: 10.1039/c6nr03311c

  13. Influences of Carboxyl Methyl Cellulose on Performances of Mortar

    Institute of Scientific and Technical Information of China (English)

    WANG Yuli; ZHOU Mingkai; SHAN Junhong; XU Fang; YANG Yuhui

    2007-01-01

    Carboxyl methyl cellulose (CMC) was mixed into mortar to improve the waterretention performance of mortar, the quality of floated coat of aerated concrete became better. The consistency and compression strength of mortar with CMC were studied. The water absorption was studied with the method of filter paper. The micro mechanism was researched with X-ray diffraction and scanning electron microscopy(SEM). The experimental results show the water-holding performance of mortar with CMC is largely improved and it is better when the mixed amount is about 1.5%; the compression strength had a descending trend with the increase of CMC; CMC reacted with calcium hydroxide(CH) into the deposition of calcium carboxyl methyl cellulose.

  14. Fluorescently tuned nitrogen-doped carbon dots from carbon source with different content of carboxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hao; Wang, Yun; Dai, Xiao; Zou, Guifu, E-mail: kqzhang@suda.edu.cn, E-mail: zouguifu@suda.edu.cn [College of Physics, Optoelectronics and Energy and Collaborative Innovation Center of Suzhou Nano Science and Technology, Soochow University, Suzhou 215006 (China); Gao, Peng; Zhang, Ke-Qin, E-mail: kqzhang@suda.edu.cn, E-mail: zouguifu@suda.edu.cn; Du, Dezhuang [National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou 215123 (China); Guo, Jun [Testing and Analysis Center, Soochow University, Suzhou 215123 (China)

    2015-08-01

    In this study, fluorescent nitrogen-doped carbon dots (NCDs) were tuned via varying the sources with different number of carboxyl groups. Owing to the interaction between amino and carboxyl, more amino groups conjugate the surface of the NCDs by the source with more carboxyl groups. Fluorescent NCDs were tuned via varying the sources with different content of carboxyl groups. Correspondingly, the nitrogen content, fluorescence quantum yields and lifetime of NCDs increases with the content of carboxyl groups from the source. Furthermore, cytotoxicity assay and cell imaging test indicate that the resultant NCDs possess low cytotoxicity and excellent biocompatibility.

  15. Fluorescently tuned nitrogen-doped carbon dots from carbon source with different content of carboxyl groups

    International Nuclear Information System (INIS)

    In this study, fluorescent nitrogen-doped carbon dots (NCDs) were tuned via varying the sources with different number of carboxyl groups. Owing to the interaction between amino and carboxyl, more amino groups conjugate the surface of the NCDs by the source with more carboxyl groups. Fluorescent NCDs were tuned via varying the sources with different content of carboxyl groups. Correspondingly, the nitrogen content, fluorescence quantum yields and lifetime of NCDs increases with the content of carboxyl groups from the source. Furthermore, cytotoxicity assay and cell imaging test indicate that the resultant NCDs possess low cytotoxicity and excellent biocompatibility

  16. Use of potassium-form cation-exchange resin as a conductimetric enhancer in ion-exclusion chromatography of aliphatic carboxylic acids.

    Science.gov (United States)

    Iwata, Tomotaka; Mori, Masanobu; Itabashi, Hideyuki; Tanaka, Kazuhiko

    2009-09-15

    In this study, a cation-exchange resin (CEX) of the K(+)-form, i.e., an enhancer resin, is used as a postcolumn conductimetric enhancer in the ion-exclusion chromatography of aliphatic carboxylic acids. The enhancer resin is filled in the switching valve of an ion chromatograph; this valve is usually used as a suppressor valve in ion-exchange chromatography. An aliphatic carboxylic acid (e.g., CH(3)COOH) separated by a weakly acidic CEX column of the H(+)-form converts into that of the K(+)-form (e.g., CH(3)COOK) by passing through the enhancer resin. In contrast, the background conductivity decreases because a strong acid (e.g., HNO(3)) with a higher conductimetric response in an eluent converts into a salt (e.g., KNO(3)) with a lower conductimetric response. Since the pH of the eluent containing the resin enhancer increases from 3.27 to 5.85, the enhancer accelerates the dissociations of analyte acids. Consequently, peak heights and peak areas of aliphatic carboxylic acids (e.g., acetic acid, propionic acid, butyric acid, and valeric acid) with the enhancer resin are 6.3-8.0 times higher and 7.2-9.2 times larger, respectively, than those without the enhancer resin. Calibrations of peak areas for injected analytes are linear in the concentration range of 0.01-1.0mM. The detection limits (signal-to-noise ratio=3) range from 0.10 microM to 0.39 microM in this system, as opposed to those in the range of 0.24-7.1 microM in the separation column alone. The developed system is successfully applied to the determination of aliphatic carboxylic acids in a chicken droppings sample. PMID:19615503

  17. The concise synthesis of chiral tfb ligands and their application to the rhodium-catalyzed asymmetric arylation of aldehydes

    OpenAIRE

    Nishimura, Takahiro; Kumamoto, Hana; Nagaosa, Makoto; Hayashi, Tamio

    2009-01-01

    New C2-symmetric tetrafluorobenzobarrelene ligands were prepared and applied successfully to the rhodium-catalyzed asymmetric addition of arylboronic acids to aromatic aldehydes giving chiral diarylmethanols in high yield with high enantioselectivity.

  18. Enantioselective Pinacol Coupling of Aromatic Aldehydes Mediated by TiCl4(THF)2/Zn with Tartaric Ester

    Institute of Scientific and Technical Information of China (English)

    LI You-Gui李有桂; JIANG Chen江辰; ZHAO Jun赵俊; TIAN Qing-Shan田青杉; YOU Tian-Pa尤田耙

    2004-01-01

    Asymmetric pinacol coupling of aromatic aldehydes mediated by low valent titanium complexes of chiral ligands derived from natural tartaric acid provided corresponding pinacols in good yields with excellent diastereoselectivities and moderate enantioselectivities.

  19. New Aldehyde Reductase Genes of Saccharomyces cerevisiae Contribute In Situ Detoxification of Lignocellulose-to-Ethanol Conversion Inhibitiors

    Science.gov (United States)

    Furfural and 5-hydroxymethylfurfural (HMF) are inhibitory compounds commonly encountered during lignocellulose-to-ethanol conversion for cleaner transportation fuels. It is possible to in situ detoxify the aldehyde inhibitors by tolerant ethanologenic yeast strains. Multiple gene-mediated reductio...

  20. Synthesis of chiral N-ferrocenylmethylaminoalcohols and their applica-tion in enantioselective addition of diethylzinc to aldehydes

    Institute of Scientific and Technical Information of China (English)

    Jian Feng GE; Zong Xuan SHEN; Ya Wen ZHANG

    2004-01-01

    Three chiral N-ferrocenylmethylaminoalcohols were synthesized from readily available natural L-valine, leucine and phenylanine, and used as chiral ligands in the enantioselective addition of diethylzinc to aldehydes.

  1. Therapeutic potential of targeting lipid aldehydes and lipoxidation end-products in the treatment of ocular disease.

    Science.gov (United States)

    McDowell, Rosemary E; McGeown, J Graham; Stitt, Alan W; Curtis, Tim M

    2013-02-01

    Lipoxidation reactions and the subsequent accumulation of advanced lipoxidation end products (ALEs) have been implicated in the pathogenesis of many of the leading causes of visual impairment. Here, we begin by outlining some of the major lipid aldehydes produced through lipoxidation reactions, the ALEs formed upon their reaction with proteins, and the endogenous aldehyde metabolizing enzymes involved in protecting cells against lipoxidation mediated damage. Discussions are subsequently focused on the clinical and experimental evidence supporting the contribution of lipid aldehydes and ALEs in the development of ocular diseases. From these discussions, it is clear that inhibition of lipoxidation reactions and ALE formation could represent a new therapeutic avenue for the treatment of a broad range of ocular disorders. Current and emerging pharmacological strategies to prevent or neutralize the effects of lipid aldehydes and ALEs are therefore considered, with particular emphasis on the potential of these drugs for treatment of diseases of the eye. PMID:23360143

  2. The Genetics of Alcohol Metabolism: Role of Alcohol Dehydrogenase and Aldehyde Dehydrogenase Variants

    OpenAIRE

    Edenberg, Howard J

    2007-01-01

    The primary enzymes involved in alcohol metabolism are alcohol dehydrogenase (ADH) and aldehyde dehydrogenase (ALDH). Both enzymes occur in several forms that are encoded by different genes; moreover, there are variants (i.e., alleles) of some of these genes that encode enzymes with different characteristics and which have different ethnic distributions. Which ADH or ALDH alleles a person carries influence his or her level of alcohol consumption and risk of alcoholism. Researchers to date pri...

  3. High aldehyde dehydrogenase activity identifies cancer stem cells in human cervical cancer

    OpenAIRE

    Liu, Shu-Yan; Zheng, Peng-Sheng

    2013-01-01

    High aldehyde dehydrogenase (ALDH) activity characterizes a subpopulation of cells with cancer stem cell (CSC) properties in several malignancies. To clarify whether ALDH can be used as a marker of cervical cancer stem cells (CCSCs), ALDHhigh and ALDHlow cells were sorted from 4 cervical cancer cell lines and 5 primary tumor xenografts and examined for CSC characteristics. Here, we demonstrate that cervical cancer cells with high ALDH activity fulfill the functional criteria for CSCs: (1) ALD...

  4. Aldehyde Dehydrogenase 1 Is a Tumor Stem Cell-Associated Marker in Lung Cancer

    OpenAIRE

    Jiang, Feng; Qiu, Qi; Khanna, Abha; Todd, Nevins W.; Deepak, Janaki; Xing, Lingxiao; Wang, Huijun; Liu, Zhenqiu; Su, Yun; Stass, Sanford A.; Katz, Ruth L

    2009-01-01

    Tumor contains small population of cancer stem cells (CSC) that are responsible for its maintenance and relapse. Analysis of these CSCs may lead to effective prognostic and therapeutic strategies for the treatment of cancer patients. We report here the identification of CSCs from human lung cancer cells using Aldefluor assay followed by fluorescence-activated cell sorting analysis. Isolated cancer cells with relatively high aldehyde dehydrogenase 1 (ALDH1) activity display in vitro features o...

  5. Aqueous DMSO Mediated Conversion of (2-(Arylsulfonyl)vinyl)iodonium Salts to Aldehydes and Vinyl Chlorides.

    Science.gov (United States)

    Zawia, Eman; Moran, Wesley J

    2016-01-01

    Vinyl(aryl)iodonium salts are useful compounds in organic synthesis but they are under-utilized and their chemistry is under-developed. Herein is described the solvolysis of some vinyl(phenyl)iodonium salts, bearing an arylsulfonyl group, in aqueous DMSO leading to aldehyde formation. This unusual process is selective and operates under ambient conditions. Furthermore, the addition of aqueous HCl and DMSO to these vinyl(aryl)iodonium salts allows their facile conversion to vinyl chlorides. PMID:27537866

  6. Alcohol and Aldehyde Dehydrogenases: Retinoid Metabolic Effects in Mouse Knockout Models

    OpenAIRE

    Kumar, Sandeep; Sandell, Lisa L.; Trainor, Paul A; Koentgen, Frank; Duester, Gregg

    2011-01-01

    Retinoic acid (RA) is the active metabolite of vitamin A (retinol) that controls growth and development. The first step of RA synthesis is controlled by enzymes of the alcohol dehydrogenase (ADH) and retinol dehydrogenase (RDH) families that catalyze oxidation of retinol to retinaldehyde. The second step of RA synthesis is controlled by members of the aldehyde dehydrogenase (ALDH) family also known as retinaldehyde dehydrogenase (RALDH) that further oxidize retinaldehyde to produce RA. RA fun...

  7. Genotoxic consequences of endogenous aldehydes on mouse haematopoietic stem cell function.

    Science.gov (United States)

    Garaycoechea, Juan I; Crossan, Gerry P; Langevin, Frederic; Daly, Maria; Arends, Mark J; Patel, Ketan J

    2012-09-27

    Haematopoietic stem cells (HSCs) regenerate blood cells throughout the lifespan of an organism. With age, the functional quality of HSCs declines, partly owing to the accumulation of damaged DNA. However, the factors that damage DNA and the protective mechanisms that operate in these cells are poorly understood. We have recently shown that the Fanconi anaemia DNA-repair pathway counteracts the genotoxic effects of reactive aldehydes. Mice with combined inactivation of aldehyde catabolism (through Aldh2 knockout) and the Fanconi anaemia DNA-repair pathway (Fancd2 knockout) display developmental defects, a predisposition to leukaemia, and are susceptible to the toxic effects of ethanol-an exogenous source of acetaldehyde. Here we report that aged Aldh2(-/-) Fancd2(-/-) mutant mice that do not develop leukaemia spontaneously develop aplastic anaemia, with the concomitant accumulation of damaged DNA within the haematopoietic stem and progenitor cell (HSPC) pool. Unexpectedly, we find that only HSPCs, and not more mature blood precursors, require Aldh2 for protection against acetaldehyde toxicity. Additionally, the aldehyde-oxidizing activity of HSPCs, as measured by Aldefluor stain, is due to Aldh2 and correlates with this protection. Finally, there is more than a 600-fold reduction in the HSC pool of mice deficient in both Fanconi anaemia pathway-mediated DNA repair and acetaldehyde detoxification. Therefore, the emergence of bone marrow failure in Fanconi anaemia is probably due to aldehyde-mediated genotoxicity restricted to the HSPC pool. These findings identify a new link between endogenous reactive metabolites and DNA damage in HSCs, and define the protective mechanisms that counteract this threat. PMID:22922648

  8. Protein alkylation by the α,β-unsaturated aldehyde acrolein. A reversible mechanism of electrophile signaling?

    OpenAIRE

    Randall, Matthew J.; Hristova, Milena; van der Vliet, Albert

    2013-01-01

    Acrolein, a reactive aldehyde found in cigarette smoke, is thought to induce its biological effects primarily by irreversible adduction to cellular nucleophiles such as cysteine thiols. Here, we demonstrate that acrolein rapidly inactivates the seleno-enzyme thioredoxin reductase (TrxR) in human bronchiolar epithelial HBE1 cells, which recovered over 4-8 hrs by a mechanism depending on the presence of cellular GSH and thioredoxin 1 (Trx1), and corresponding with reversal of protein-acrolein a...

  9. "Dopamine-first" mechanism enables the rational engineering of the norcoclaurine synthase aldehyde activity profile

    OpenAIRE

    Lichman, B. R.; Gershater, M. C.; Lamming, E. D.; Pesnot, T.; Sula, A.; Keep, N.H.; Hailes, H. C.; Ward, J. M.

    2015-01-01

    Norcoclaurine synthase (NCS) (EC 4.2.1.78) catalyzes the Pictet-Spengler condensation of dopamine and an aldehyde, forming a substituted (S)-tetrahydroisoquinoline, a pharmaceutically important moiety. This unique activity has led to NCS being used for both in vitro biocatalysis and in vivo recombinant metabolism. Future engineering of NCS activity to enable the synthesis of diverse tetrahydroisoquinolines is dependent on an understanding of the NCS mechanism and kinetics. We assess two propo...

  10. Three-Component Halo Aldol Condensation of Thioacrylates with Aldehydes Mediated by Titanium (IV Halide

    Directory of Open Access Journals (Sweden)

    Guigen Li

    2002-01-01

    Full Text Available a,b-Ethyl thioacrylate was difuctionalized by a tandem X-C/C=C bond formation reaction. The new system uses Ti (IV halide as both the Lewis acidic promoter and the halogen source for the Michael-type addition onto the thioacrylate. The titanium enolate species resulting from Michael-type addition react with aldehydes followed by dehydration to afford trisubstituted olefin products. Complete geometric selectivity (>95% and up to 72% yield have been obtained for 7 examples.

  11. Three-Component Halo Aldol Condensation of Thioacrylates with Aldehydes Mediated by Titanium (IV) Halide

    OpenAIRE

    Guigen Li; Gao, Joe J.; Han-Xun Wei; Sun Hee Kim

    2002-01-01

    a,b-Ethyl thioacrylate was difuctionalized by a tandem X-C/C=C bond formation reaction. The new system uses Ti (IV) halide as both the Lewis acidic promoter and the halogen source for the Michael-type addition onto the thioacrylate. The titanium enolate species resulting from Michael-type addition react with aldehydes followed by dehydration to afford trisubstituted olefin products. Complete geometric selectivity (>95%) and up to 72% yield have been obtained for 7 examples.

  12. Primary Amine–2-Aminopyrimidine Chiral Organocatalysts for the Enantioselective Conjugate Addition of Branched Aldehydes to Maleimides

    OpenAIRE

    Vizcaíno-Milla, Pascuala; Sansano Gil, José Miguel; Nájera Domingo, Carmen; Fiser, Béla; Gómez Bengoa, Enrique

    2015-01-01

    Chiral primary amines containing the (R,R)- and (S,S)-trans-cyclohexane-1,2-diamine scaffold and a pyrimidin-2-yl unit are synthesized and used as general organocatalysts for the Michael reaction of α-branched aldehydes to maleimides. The reaction takes place with 10 mol% organocatalyst loading and hexanedioic acid as cocatalyst in aqueous N,N-dimethylformamide at 10 °C affording the corresponding succinimides in good yields and enantioselectivities. DFT calculations support the stereochemica...

  13. Phenolic Acids, Phenolic Aldehydes and Furanic Derivatives in Oak Chips: American vs. French Oaks

    OpenAIRE

    Cabrita, M.J.; Barrocas Dias, C.; Costa Freitas, A.M.

    2011-01-01

    Phenolic acids (gallic, vanillic, syringic and ellagic acids), phenolic aldehydes (vanillin, syringaldehyde, coniferaldehyde and sinapaldehyde) and furanic derivatives (furfural, 5-methylfurfural and 5-hydroxymethylfurfural) were quantified in commercial American and French oak chips. Chips with different sizes and toast degrees were used. Compounds were extracted directly from the wood samples in order to determine possible differences among woods as well as toast degree. Likewise, the compo...

  14. Ambient concentrations of aldehydes in relation to Beijing Olympic air pollution control measures

    Directory of Open Access Journals (Sweden)

    J. C. Gong

    2010-08-01

    Full Text Available Aldehydes are ubiquitous constituents of the atmosphere. Their concentrations are elevated in polluted urban atmospheres. The present study was carried out to characterize three aldehydes of most health concern (formaldehyde, acetaldehyde, and acrolein in a central Beijing site in the summer and early fall of 2008 (from June to October. Measurements were made before, during, and after the Beijing Olympics to examine whether the air pollution control measures implemented to improve Beijing's air quality during the Olympics had any impact on concentrations of the three aldehydes. Average concentrations of formaldehyde, acetaldehyde and acrolein were 29.34 ± 15.12 μg/m3, 27.09 ± 15.74 μg/m3 and 2.32 ± 0.95 μg/m3, respectively, for the entire period of measurements, all being the highest among the levels measured in cities around the world in photochemical smog seasons. Among the three measured aldehydes, only acetaldehyde had a substantially reduced mean concentration during the Olympic air pollution control period compared to the pre-Olympic period. Formaldehyde and acrolein followed the changing pattern of temperature and were each significantly correlated with ozone (a secondary product of photochemical reactions. In contrast, acetaldehyde was significantly correlated with several pollutants emitted mainly from local emission sources (e.g., NO2, CO, and PM2.5. These findings suggest that local direct emissions had a larger impact on acetaldehyde than formaldehyde and acrolein.

  15. Revisiting the Reaction Between Diaminomaleonitrile and Aromatic Aldehydes: a Green Chemistry Approach

    OpenAIRE

    Francisco León; Jaime Ríos-Motta Ríos-Motta; Augusto Rivera

    2006-01-01

    The reaction between diaminomaleonitrile (DAMN) and aldehydes and the resulting monoimines are well known. Since the standard reaction conditions involve the use of toxic solvents (typically methanol), we have sought to apply green chemistry principles to this reaction by either using water as the solvent without any catalysts or employing “solvent-free†conditions. The monoimines derived from DAMN are of interest as precursors for obtaining different heterocyclic systems and linear ...

  16. Aldehydes in relation to air pollution sources: A case study around the Beijing Olympics

    Science.gov (United States)

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

    2015-05-01

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

  17. Roles of histamine on the expression of aldehyde dehydrogenase 1 in endometrioid adenocarcinoma cell line

    OpenAIRE

    Wang, Yi; Jiang, Yang; IKEDA, JUN-ICHIRO; TIAN, TIAN; Sato, Atsushi; Ohtsu, Hiroshi; Morii, Eiichi

    2014-01-01

    Cancer-initiating cells (CICs) are a limited number of cells that are essential for maintenance, recurrence, and metastasis of tumors. Aldehyde dehydrogenase 1 (ALDH1) has been recognized as a marker of CICs. We previously reported that ALDH1-high cases of uterine endometrioid adenocarcinoma showed poor prognosis, and that ALDH1 high population was more tumorigenic, invasive, and resistant to apoptosis than ALDH1 low population. Histamine plays a critical role in cancer cell proliferation, mi...

  18. Complex formation of Np(V) with various carboxylates

    International Nuclear Information System (INIS)

    The stability constants of Np(V) complexes with a series of aliphatic and aromatic carboxylates, including hydroxycarboxylates, hydroxydicarboxylates, dicarboxylates and pyridinecarboxylates have been obtained in 1.0 M NaClO4 by a solvent extraction method using thenoyltrifluoroacetone and 1,10- phenanthroline in isoamyl alcohol. Stabilities of these complexes are discussed in terms of their structures and ligand basicities. (orig.)

  19. Enhancing magnetoresistance in tetrathiafulvalene carboxylate modified iron oxide nanoparticle assemblies.

    Science.gov (United States)

    Lv, Zhong-Peng; Luan, Zhong-Zhi; Cai, Pei-Yu; Wang, Tao; Li, Cheng-Hui; Wu, Di; Zuo, Jing-Lin; Sun, Shouheng

    2016-06-16

    We report a facile approach to stabilize Fe3O4 nanoparticles (NPs) by using tetrathiafulvalene carboxylate (TTF-COO(-)) and to control electron transport with an enhanced magnetoresistance (MR) effect in TTF-COO-Fe3O4 NP assemblies. This TTF-COO-coating is advantageous over other conventional organic coatings, making it possible to develop stable Fe3O4 NP arrays for sensitive spintronics applications. PMID:27271347

  20. Circulating Nonphosphorylated Carboxylated Matrix Gla Protein Predicts Survival in ESRD

    OpenAIRE

    Schlieper, Georg; Westenfeld, Ralf; Krüger, Thilo; Cranenburg, Ellen C.; Magdeleyns, Elke J.; Brandenburg, Vincent M.; Djuric, Zivka; Damjanovic, Tatjana; Ketteler, Markus; Vermeer, Cees; Dimkovic, Nada; Floege, Jürgen; Schurgers, Leon J.

    2011-01-01

    The mechanisms for vascular calcification and its associated cardiovascular mortality in patients with ESRD are not completely understood. Dialysis patients exhibit profound vitamin K deficiency, which may impair carboxylation of the calcification inhibitor matrix gla protein (MGP). Here, we tested whether distinct circulating inactive vitamin K–dependent proteins associate with all-cause or cardiovascular mortality. We observed higher levels of both desphospho-uncarboxylated MGP (dp-ucMGP) a...

  1. Crystal structure of ethyl 2,4-dichloroquinoline-3-carboxylate

    Directory of Open Access Journals (Sweden)

    Alberto Cabrera

    2015-12-01

    Full Text Available In the crystal structure of the title compound, C12H9Cl2NO2, the mean planes through the quinoline and carboxylate groups have r.m.s. deviations of 0.006 and 0.021 Å, respectively, and form a dihedral angle of 87.06 (19°. In the crystal, molecules are linked via very weak C—H...O hydrogen bonds, forming chains, which propagate along the c-axis direction.

  2. Carboxylate Shifts Steer Interquinone Electron Transfer in Photosynthesis*

    OpenAIRE

    Chernev, Petko; Zaharieva, Ivelina; Dau, Holger; Haumann, Michael

    2010-01-01

    Understanding the mechanisms of electron transfer (ET) in photosynthetic reaction centers (RCs) may inspire novel catalysts for sunlight-driven fuel production. The electron exit pathway of type II RCs comprises two quinone molecules working in series and in between a non-heme iron atom with a carboxyl ligand (bicarbonate in photosystem II (PSII), glutamate in bacterial RCs). For decades, the functional role of the iron has remained enigmatic. We tracked the iron site using microsecond-resolu...

  3. Block and Graft Copolymers Containing Carboxylate or Phosphonate Anions

    OpenAIRE

    Hu, Nan

    2014-01-01

    This dissertation focuses on synthesis and characterization of graft and block copolymers containing carboxylate or phosphonate anions that are potential candidates for biomedical applications such as drug delivery and dental adhesives. Ammonium bisdiethylphosphonate (meth)acrylate and acrylamide phosphonate monomers were synthesized based on aza-Michael addition reactions. Free radical copolymerizations of these monomers with an acrylate-functional poly(ethylene oxide) (PEO) macromonomer...

  4. Electrochemical cell studies on fluorinated natural graphite in propylene carbonate electrolyte with difluoromethyl acetate (MFA) additive for low temperature lithium battery application

    Indian Academy of Sciences (India)

    R Chandrasekaran; M Koh; Y Ozhawa; H Aaoyoma; T Nakajima

    2009-05-01

    Electrochemical cell performances of fluorinated natural graphite (abbreviated as FNG) electrode material was studied by using 1M of LiClO4- EC : DEC : PC (1 : 1 : 1 v%) electrolyte solution with and without 0.15% v/v fluorinated carboxylic ester additive difluoromethyl acetate-CHF2COOCH3 (MFA) at -10°C. The electrochemical cell performances were studied by cyclic voltammetry, galvanostatic charge-discharge and impedance analysis. The additive has proven its positive role with the electrolyte system and has shown the improved characterization over the blank electrolyte system.

  5. "Protective Effects of Some Azo Derivatives of 5-aminosalicylic Acid and Their Pegylated Prodrugs on Acetic Acid-induced Rat Colitis "

    OpenAIRE

    Alireza Garjani; Soodabeh Davaran; Mohamadreza Rashidi; Nasrin Malek

    2004-01-01

    The protective and anti-inflammatory effects of azo and azo-linked polymeric prodrugs of 5-aminosalicylic acid (5-ASA) on acetic acid induced colitis in rats were investigated. Three azo prodrugs; 4,4 -dihydroxy-azobenzene-3-carboxilic acid (azo compound I), 4-hydroxy-azobenzene-3,4-dicarboxilic acid (azo compound II), 4,4-dihydroxy-3-formyl-azobenzene-3-carboxylic acid (azo compound III) and their polyethylene glycol (PEG 6000) derivatives were synthesized. Rats were pretreated orally (1 hou...

  6. Breast cancer and depot-medroxyprogesterone acetate

    OpenAIRE

    1985-01-01

    The preliminary results of a study of the incidence of breast cancer in relation to use of depot-medroxyprogesterone acetate (DMPA) are presented. The findings are based on data from three participating centres in Thailand, and one each in Kenya and Mexico. A relative risk for breast cancer of 0.7 was observed in women who had ever used DMPA; this was not statistically significant. Although no consistent decrease in risk with duration of use was observed, the lowest relative risk (0.5) was ob...

  7. Carboxylic acid-functionalized SBA-15 nanorods for gemcitabine delivery

    International Nuclear Information System (INIS)

    The present study deals with the functionalization of mesoporous silica nanoparticles as drug delivery systems. Mono, di, and tri amino-functionalized SBA-15 nanorods were synthesized by post-grafting method using (3-aminopropyl) triethoxysilane, N-(2-aminoethyl-)3- aminopropyltrimethoxysilane, and 3-[2-(2-aminoethylamino) ethylamino] propyl trimethoxysilane, respectively. The carboxylic acid derivatives of the amino-functionalized samples were obtained using succinic anhydride. Tminopropyltrimethoxysilanehe obtained modified materials were investigated as matrixes for the anticancer drug (gemcitabine) delivery. The prepared samples were characterized by SAXS, N2 adsorption/desorption, SEM, transmission electron microscopy, thermogravimetric analysis, and FTIR and UV spectroscopies. The adsorption and release properties of all samples were studied. It was revealed that the adsorption capacity and release behavior of gemcitabine were highly dependent on the type of the introduced functional groups. The carboxylic acid-modified samples have higher loading content, due to the strong interaction with gemcitabine. The maximum content of deposited drug in the modified SBA-15 nanorods is close to 40 wt%. It was found that the surface functionalization leads toward significant decrease of the drug release rate. The carboxylic acid-functionalized samples have slower release rate in contrast with the amino-functionalized samples

  8. Biarylalkyl Carboxylic Acid Derivatives as Novel Antischistosomal Agents.

    Science.gov (United States)

    Mäder, Patrick; Blohm, Ariane S; Quack, Thomas; Lange-Grünweller, Kerstin; Grünweller, Arnold; Hartmann, Roland K; Grevelding, Christoph G; Schlitzer, Martin

    2016-07-01

    Parasitic platyhelminths are responsible for serious infectious diseases, such as schistosomiasis, which affect humans as well as animals across vast regions of the world. The drug arsenal available for the treatment of these diseases is limited; for example, praziquantel is the only drug currently used to treat ≥240 million people each year infected with Schistosoma spp., and there is justified concern about the emergence of drug resistance. In this study, we screened biarylalkyl carboxylic acid derivatives for their antischistosomal activity against S. mansoni. These compounds showed significant influence on egg production, pairing stability, and vitality. Tegumental lesions or gut dilatation was also observed. Substitution of the terminal phenyl residue in the biaryl scaffold with a 3-hydroxy moiety and derivatization of the terminal carboxylic acid scaffold with carboxamides yielded compounds that displayed significant antischistosomal activity at concentrations as low as 10 μm with satisfying cytotoxicity values. The present study provides detailed insight into the structure-activity relationships of biarylalkyl carboxylic acid derivatives and thereby paves the way for a new drug-hit moiety for fighting schistosomiasis. PMID:27159334

  9. ELECTROANALYTICAL APPLICATIONS OF CARBOXYL-MODIFIED CARBON NANOTUBE FILM ELECTRODES

    Institute of Scientific and Technical Information of China (English)

    C.G. Hu; W.L. Wang; K.J. Liao; W. Zhu

    2003-01-01

    The electrochemical behavior of a carboxyl-modified carbon nanotube films was investigated to explore its possibility in electroanalytical applicaton. Cyclic voltammetry of quinone was conducted in 1mol/L Na2SO4, which showed a stable, quasi-reversible voltammetric response for quinone / hydroquinone, and the anodic and the cathodic peak potentials were 0.657V and -0.029V (vs. SCE) at a scan rate of 0.1V.s-1, respectively. Both anodic and cathodic peak currents depended linearly on the square root of the scan rate over the range of 0.01-0. 5 V.s-1, which suggested that the process of the electrode reactions was diffusion-controlled. Carboxyl-modified carbon nanotube electrodes made it possible to determine low level of dopamine selectively in the presence of a large excess of ascorbic acid in acidic media using derivative voltammetry.The results obtained were discussed in details. This work demonstrates the potential of carboxyl-modified carbon nanotube electrodes for electroanalytical applications.

  10. Cellular uptake and anticancer activity of carboxylated gallium corroles.

    Science.gov (United States)

    Pribisko, Melanie; Palmer, Joshua; Grubbs, Robert H; Gray, Harry B; Termini, John; Lim, Punnajit

    2016-04-19

    We report derivatives of gallium(III) tris(pentafluorophenyl)corrole, 1 [Ga(tpfc)], with either sulfonic (2) or carboxylic acids (3, 4) as macrocyclic ring substituents: the aminocaproate derivative, 3 [Ga(ACtpfc)], demonstrated high cytotoxic activity against all NCI60 cell lines derived from nine tumor types and confirmed very high toxicity against melanoma cells, specifically the LOX IMVI and SK-MEL-28 cell lines. The toxicities of 1, 2, 3, and 4 [Ga(3-ctpfc)] toward prostate (DU-145), melanoma (SK-MEL-28), breast (MDA-MB-231), and ovarian (OVCAR-3) cancer cells revealed a dependence on the ring substituent: IC50values ranged from 4.8 to >200 µM; and they correlated with the rates of uptake, extent of intracellular accumulation, and lipophilicity. Carboxylated corroles 3 and 4, which exhibited about 10-fold lower IC50values ( 3 > 2 > 1 (intracellular accumulation of gallium corroles was fastest in melanoma cells). We conclude that carboxylated gallium corroles are promising chemotherapeutics with the advantage that they also can be used for tumor imaging. PMID:27044076

  11. Carboxylic acid-functionalized SBA-15 nanorods for gemcitabine delivery

    Energy Technology Data Exchange (ETDEWEB)

    Bahrami, Zohreh; Badiei, Alireza, E-mail: abadiei@khayam.ut.ac.ir [University of Tehran, School of Chemistry, College of Science (Iran, Islamic Republic of); Ziarani, Ghodsi Mohammadi [Alzahra University, Research Laboratory of Pharmaceutical (Iran, Islamic Republic of)

    2015-03-15

    The present study deals with the functionalization of mesoporous silica nanoparticles as drug delivery systems. Mono, di, and tri amino-functionalized SBA-15 nanorods were synthesized by post-grafting method using (3-aminopropyl) triethoxysilane, N-(2-aminoethyl-)3- aminopropyltrimethoxysilane, and 3-[2-(2-aminoethylamino) ethylamino] propyl trimethoxysilane, respectively. The carboxylic acid derivatives of the amino-functionalized samples were obtained using succinic anhydride. Tminopropyltrimethoxysilanehe obtained modified materials were investigated as matrixes for the anticancer drug (gemcitabine) delivery. The prepared samples were characterized by SAXS, N{sub 2} adsorption/desorption, SEM, transmission electron microscopy, thermogravimetric analysis, and FTIR and UV spectroscopies. The adsorption and release properties of all samples were studied. It was revealed that the adsorption capacity and release behavior of gemcitabine were highly dependent on the type of the introduced functional groups. The carboxylic acid-modified samples have higher loading content, due to the strong interaction with gemcitabine. The maximum content of deposited drug in the modified SBA-15 nanorods is close to 40 wt%. It was found that the surface functionalization leads toward significant decrease of the drug release rate. The carboxylic acid-functionalized samples have slower release rate in contrast with the amino-functionalized samples.

  12. Green process for chemical functionalization of nanocellulose with carboxylic acids.

    Science.gov (United States)

    Espino-Pérez, Etzael; Domenek, Sandra; Belgacem, Naceur; Sillard, Cécile; Bras, Julien

    2014-12-01

    An environmentally friendly and simple method, named SolReact, has been developed for a solvent-free esterification of cellulose nanocrystals (CNC) surface by using two nontoxic carboxylic acids (CA), phenylacetic acid and hydrocinnamic acid. In this process, the carboxylic acids do not only act as grafting agent, but also as solvent media above their melting point. Key is the in situ solvent exchange by water evaporation driving the esterification reaction without drying the CNC. Atomic force microscopy and X-ray diffraction analyses showed no significant change in the CNC dimensions and crystallinity index after this green process. The presence of the grafted carboxylic was characterized by analysis of the "bulk" CNC with elemental analysis, infrared spectroscopy, and (13)C NMR. The ability to tune the surface properties of grafted nanocrystals (CNC-g-CA) was evaluated by X-ray photoelectron spectroscopy analysis. The hydrophobicity behavior of the functionalized CNC was studied through the water contact-angle measurements and vapor adsorption. The functionalization of these bionanoparticles may offer applications in composite manufacturing, where these nanoparticles have limited dispersibility in hydrophobic polymer matrices and as nanoadsorbers due to the presence of phenolic groups attached on the surface. PMID:25353612

  13. Reaction of arylsulfonylhydrazones of aldehydes with alpha-magnesio sulfones. A novel olefin synthesis.

    Science.gov (United States)

    Kurek-Tyrlik, A; Marczak, S; Michalak, K; Wicha, J; Zarecki, A

    2001-10-19

    Reactions of representative tosylhydrazones of aldehydes and ketones with alpha-metalated sulfones were examined in order to develop a practical olefination method. Treatment of aldehyde tosylhydrazone 2 with an excess of alpha-lithiated methyl phenyl or dimethyl sulfones yielded 3a. The reaction of 2 with sterically unhindered lithiated alkyl sulfones gave mixtures of the respective olefination products 3b-d along with the Shapiro fragmentation product 4. Sterically hindered lithiated sulfones afforded Shapiro products exclusively. In contrast, aldehyde tosylhydrazones 2 or 6 in reactions with a variety of alpha-magnesio primary or secondary alkyl sulfones gave olefination products 3a-j and 7a-c in high yields (Tables 1 and 2). beta-Branched alkyl sulfones afforded predominantly (E)-alkenes, whereas unhindered primary sulfones gave mixtures of (E)- and (Z)-alkenes with low selectivity. Reaction of the 2,4,6-triisopropylbenzenesulfonylhydrazone (trisylhydrazone) of cyclodecanone 11c with alpha-magnesio methyl phenyl sulfone afforded the methylidene derivative 12a contaminated with the Shapiro product 13. Tosylhydrazone 2 resisted reaction with i-PrMgCl and gave only a small amount of the addition product in reaction with Bu(2)Mg. Some mechanistic aspects of the reaction of tosylhydrazones with organomagnesium compounds are discussed. PMID:11597219

  14. Aldehydes, hydrogen peroxide, and organic radicals as mediators of ozone toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Pryor, W.A.; Church, D.F. (Biodynamics Institute, Louisiana State University, Baton Rouge (United States))

    1991-01-01

    It is generally agreed that unsaturated fatty acids (UFA) are an important class of target molecule for reaction with ozone when polluted air is inhaled. Most discussions have implicated the UFA in cell membranes, but lung lining fluids also contain fatty acids that are from 20 to 40% unsaturated. Since UFA in lung lining fluids exist in a highly aquated environment, ozonation would be expected to produce aldehydes and hydrogen peroxide, rather than the Criegee ozonide. In agreement with this expectation, the authors find that ozonations of emulsions of fatty acids containing from one to four double bonds give one mole of H2O2 for each mole of ozone reacted. Ozonation of oleic acid emulsions and dioleoyl phosphatidyl choline gives similar results, with two moles of aldehydes and one mole of H2O2 formed per mole of ozone reacted. The net reaction that occurs when ozone reacts with pulmonary lipids is suggested to be given by equation 1. (formula: see text). From 5 to 10% yields of Criegee ozonides also appear to be formed. In addition, a direct reaction of unknown mechanism occurs between ozone and UFA in homogeneous organic solution, in homogeneous solutions in water, in aqueous emulsions, and in lipid bilayers to give organic radicals that can be spin trapped. These radicals are suggested to be responsible for initiating lipid peroxidation of polyunsaturated fatty acids. Thus, aldehydes, hydrogen peroxide, and directly produced organic radicals are suggested to be mediators of ozone-induced pathology.39 references.

  15. Hydrazide and hydrazine reagents as reactive matrices for MALDI-MS to detect gaseous aldehydes.

    Science.gov (United States)

    Shigeri, Yasushi; Ikeda, Shinya; Yasuda, Akikazu; Ando, Masanori; Sato, Hiroaki; Kinumi, Tomoya

    2014-08-01

    The reagents 19 hydrazide and 14 hydrazine were examined to function as reactive matrices for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) to detect gaseous aldehydes. Among them, two hydrazide (2-hydroxybenzohydrazide and 3-hydroxy-2-naphthoic acid hydrazide) and two hydrazine reagents [2-hydrazinoquinoline and 2,4-dinitrophenylhydrazine (DNPH)] were found to react efficiently with carbonyl groups of gaseous aldehydes (formaldehyde, acetaldehyde and propionaldehyde); these are the main factors for sick building syndrome and operate as reactive matrices for MALDI-MS. Results from accurate mass measurements by JMS-S3000 Spiral-TOF suggested that protonated ion peaks corresponding to [M + H](+) from the resulting derivatives were observed in all cases with the gaseous aldehydes in an incubation, time-dependent manner. The two hydrazide and two hydrazine reagents all possessed absorbances at 337 nm (wavelength of MALDI nitrogen laser), with, significant electrical conductivity of the matrix crystal and functional groups, such as hydroxy group and amino group, being important for desorption/ionization efficiency in MALDI-MS. To our knowledge, this is the first report that gaseous molecules could be derivatized and detected directly in a single step by MALDI-MS using novel reactive matrices that were derivatizing agents with the ability to enhance desorption/ionization efficiency. PMID:25044902

  16. Pulsed corona discharge oxidation of aqueous lignin: decomposition and aldehydes formation.

    Science.gov (United States)

    Panorel, Iris; Kaijanen, Laura; Kornev, Iakov; Preis, Sergei; Louhi-Kultanen, Marjatta; Sirén, Heli

    2014-01-01

    Lignin is the mass waste product of pulp and paper industry mostly incinerated for energy recovery. Lignin is, however, a substantial source of raw material for derivatives currently produced in costly wet oxidation processes. The pulsed corona discharge (PCD) for the first time was applied to lignin oxidation aiming a cost-effective environmentally friendly lignin removal and transformation to aldehydes. The experimental research into treatment of coniferous kraft lignin aqueous solutions was undertaken to establish the dependence of lignin oxidation and aldehyde formation on the discharge parameters, initial concentration of lignin and gas phase composition. The rate and the energy efficiency of lignin oxidation increased with increasing oxygen concentration reaching up to 82 g kW-1 h-1 in 89% vol. oxygen. Oxidation energy efficiency in PCD treatment exceeds the one for conventional ozonation by the factor of two under the experimental conditions. Oxidation at low oxygen concentrations showed a tendency of the increasing aldehydes and glyoxylic acid formation yield. PMID:24600854

  17. A new aldehyde oxidase catalyzing the conversion of glycolaldehyde to glycolate from Burkholderia sp. AIU 129.

    Science.gov (United States)

    Yamada, Miwa; Adachi, Keika; Ogawa, Natsumi; Kishino, Shigenobu; Ogawa, Jun; Kataoka, Michihiko; Shimizu, Sakayu; Isobe, Kimiyasu

    2015-04-01

    We found a new aldehyde oxidase (ALOD), which catalyzes the conversion of glycolaldehyde to glycolate, from Burkholderia sp. AIU 129. The enzyme further oxidized aliphatic aldehydes, an aromatic aldehyde, and glyoxal, but not glycolate or alcohols. The molecular mass of this enzyme was 130 kDa, and it was composed of three different subunits (αβγ structure), in which the α, β, and γ subunits were 76 kDa, 36 kDa, and 14 kDa, respectively. The N-terminal amino acid sequences of each subunit showed high similarity to those of putative subunits of xanthine dehydrogenase. Metals (copper, iron and molybdenum) and chelating reagents (α,α'-dipyridyl and 8-hydroxyquinoline) inhibited the ALOD activity. The ALOD showed highest activity at pH 6.0 and 50°C. Twenty mM glycolaldehyde was completely converted to glycolate by incubation at 30°C for 3 h, suggesting that the ALOD found in this study would be useful for enzymatic production of glycolate. PMID:25283808

  18. Crystallization and preliminary X-ray analysis of aldehyde dehydrogenase from Vibrio harveyi.

    Science.gov (United States)

    Croteau, N.; Vedadi, M.; Delarge, M.; Meighen, E.; Abu-Abed, M.; Howell, P. L.; Vrielink, A.

    1996-01-01

    Aldehyde dehydrogenase from Vibrio harveyi catalyzes the oxidation of long-chain aliphatic aldehydes to acids. The enzyme is unique among the family of aldehyde dehydrogenases in that it exhibits much higher specificity for the cofactor NADP+ than for NAD+. The sequence of this form of the enzyme varies significantly from the NAD+ dependent forms, suggesting differences in the three-dimensional structure that may be correlated to cofactor specificity. Crystals of the enzyme have been grown both in the presence and absence of NADP+ using the hanging drop vapor diffusion technique. In order to improve crystal size and quality, iterative seeding techniques were employed. The crystals belong to space group P2(1), with unit cell dimensions a = 79.4 A, b = 131.1 A, c = 92.2 A, and beta = 92.4 degrees. Freezing the crystal to 100 K has enabled a complete set of data to be collected using a rotating anode source (lambda = 1.5418 A). The crystals diffract to a minimum d-spacing of 2.6 A resolution. Based on density calculations, two homodimers of molecular weight 110 kDa are estimated to be present in the asymmetric unit. Self-rotation functions show the presence of 3 noncrystallographic twofold symmetry axes. PMID:8897616

  19. Overriding Felkin Control: A General Method for Highly Diastereoselective Chelation-Controlled Additions to α-Silyloxy Aldehydes

    OpenAIRE

    Stanton, Gretchen R.; Johnson, Corinne N.; Walsh, Patrick J.

    2010-01-01

    According to the Felkin-Anh and Cram-chelation models, nucleophilic additions to α-silyloxy aldehydes procees through a non-chelation pathway due to the steric and electronic properties of the silyl group, giving rise to Felkin addition products. Herein we describe a general method to promote chelation-control in additions to α-silyloxy aldehydes. Dialkylzincs, functionalized dialkylzincs, and (E)-disubstituted, (E)-trisubstituted, and (Z)-disubstituted vinylzinc reagents add to silyl-protect...

  20. Ethanol utilization regulatory protein: profile alignments give no evidence of origin through aldehyde and alcohol dehydrogenase gene fusion.

    OpenAIRE

    Nicholas, H B; Persson, B; Jörnvall, H; Hempel, J.

    1995-01-01

    The suggestion that the ethanol regulatory protein from Aspergillus has its evolutionary origin in a gene fusion between aldehyde and alcohol dehydrogenase genes (Hawkins AR, Lamb HK, Radford A, Moore JD, 1994, Gene 146:145-158) has been tested by profile analysis with aldehyde and alcohol dehydrogenase family profiles. We show that the degree and kind of similarity observed between these profiles and the ethanol regulatory protein sequence is that expected from random sequences of the same c...

  1. SnAP-eX Reagents for the Synthesis of Exocyclic 3-Amino- and 3-Alkoxypyrrolidines and Piperidines from Aldehydes.

    Science.gov (United States)

    Luescher, Michael U; Bode, Jeffrey W

    2016-06-01

    SnAP-eX (tin amine protocol, exocyclic heteroatoms) reagents allow the single-step transformation of aldehydes and ketones into 2,3-disubstituted pyrrolidines and piperidines containing exocyclic amine or alkoxy groups. These saturated N-heterocycles are of importance in modern drug discovery approaches and are prepared in moderate yields using an operationally simple protocol that is compatible with a range of functional groups and heterocyclic aldehydes. PMID:27192447

  2. A unified approach for the synthesis of symmetrical and unsymmetrical dibenzyl ethers from aryl aldehydes through reductive etherification

    Directory of Open Access Journals (Sweden)

    J. Sembian Ruso

    2016-05-01

    Full Text Available In this paper, we describe a simple and convenient conversion of aryl aldehydes to symmetrical dibenzyl ethers through reductive etherification. Similarly, unsymmetrical dibenzyl ether was obtained from aryl aldehyde and TES-protected benzyl alcohol. Triethyl silane with catalytic amount of InCl3 was found to be an efficient condition for the reductive etherification. Moreover, it exhibits remarkable functional group compatibility with yield ranging from good to excellent.

  3. Identification and Quantification of Aldehydes in Mezcal by Solid Phase Microextraction with On-fiber Derivatization - Gas Cromatography

    OpenAIRE

    Guadalupe Medina Valtierra; Rocío Juárez Ciprés; Araceli Peña Álvarez

    2011-01-01

    A headspace solid phase microextraction with on fiber derivatization procedure followed by gas chromatography and flame ionization detection was applied for the determination of aldehydes in mezcal. A derivatization agent o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA) was adsorbed onto a Polydimethylsiloxane/ divinyl benzene (PDMS/DVB, 65 ¿m) fiber and exposed to the headspace of a vial with a mezcal sample. The aldehydes selectively reacted with PFBHA, and the oximes were desorbed int...

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

    Science.gov (United States)

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

    2016-05-18

    In this study, the kinetics of aldehyde formation in heated frying oils was characterized by 2-hydrazinoquinoline derivatization, liquid chromatography-mass spectrometry (LC-MS) analysis, principal component analysis (PCA), and hierarchical cluster analysis (HCA). The aldehydes contributing to time-dependent separation of heated soybean oil (HSO) in a PCA model were grouped by the HCA into three clusters (A1, A2, and B) on the basis of their kinetics and fatty acid precursors. The increases of 4-hydroxynonenal (4-HNE) and the A2-to-B ratio in HSO were well-correlated with the duration of thermal stress. Chemometric and quantitative analysis of three frying oils (soybean, corn, and canola oils) and French fry extracts further supported the associations between aldehyde profiles and fatty acid precursors and also revealed that the concentrations of pentanal, hexanal, acrolein, and the A2-to-B ratio in French fry extracts were more comparable to their values in the frying oils than other unsaturated aldehydes. All of these results suggest the roles of specific aldehydes or aldehyde clusters as novel markers of the lipid oxidation status for frying oils or fried foods. PMID:27128101

  5. Simulated Solvation of Organic Ions II: Study of Linear Alkylated Carboxylate Ions in Water Nanodrops and in Liquid Water. Propensity for Air/Water Interface and Convergence to Bulk Solvation Properties.

    Science.gov (United States)

    Houriez, Céline; Meot-Ner Mautner, Michael; Masella, Michel

    2015-09-10

    We investigated the solvation of carboxylate ions from formate to hexanoate, in droplets of 50 to 1000 water molecules and neat water, by computations using standard molecular dynamics and sophisticated polarizable models. The carboxylate ions from methanoate to hexanoate show strong propensity for the air/water interface in small droplets. Only the ions larger than propanoate retain propensity for the interface in larger droplets, where their enthalpic stabilization by ion/water dispersion is reduced there by 3 kcal mol(-1) per CH2 group. This is compensated by entropy effects over +3.3 cal mol(-1) K(-1) per CH2 group. On the surface, the anionic headgroups are strongly oriented toward the aqueous core, while the hydrophobic alkyl chains are repelled into air and lose their structure-making effects. These results reproduce the structure-making effects of alkyl groups in solution, and suggest that the hydrocarbon chains of ionic headgroups and alkyl substituents solvate independently. Extrapolation to bulk solution using standard extrapolation schemes yields absolute carboxylate solvation energies. The results for formate and acetate yield a proton solvation enthalpy of about 270 kcal mol(-1), close to the experiment-based value. The largest carboxylate ions yield a value smaller by about 10 kcal mol(-1), which requires studies in much larger droplets. PMID:26287943

  6. Methylprednisolon acetate in the management of

    Directory of Open Access Journals (Sweden)

    N. Khaci, M.D.

    2008-01-01

    Full Text Available AbstractBackground and Purpose: Acute renal colic is a common complaint from patients entering the emergency departments. Although, urethral lithotripsy and extracorporeal shock wave lithotripsy are known to be effective, the role of medical-expulsive therapy for the treatment of this disease has not yet been established. This study assessed the clinical efficacy of addition methylprednisolon acetate in the medical-expulsive therapy of distal ureterolithiasis.Materials and Methods: Eighty five (85 consecutive patients with a symptomatic distal urethral stone were included in our study and randomized to one of two home treatment groups. Group A patients (n = 45 received tramadol (50mg bid and hydrochlorothiazide (50 mg daily for 21 days, and group B patients (n = 40 were treated with a corticosteroid drug (methylprednisolon acetate 40mg intra-muscular on 0, 7 and 14 days after treatment, in addition to tramadol and hydrochlorothiazide. The treatment duration was 21 days. All patients were re-evaluated after 21days with a clinical examination and KUB.Results: The mean stone size was 5.2mm and 5.8mm in groups A and B respectively (P value>0.05. Both groups had a significant difference in expulsion rate (20(44.4% for group A and 32 (88% for group B; (P value<0.001.Conclusion: Our results suggest that the use of a corticosteroid drug in association with tramadol and hydro-cholorothiazid appeared to induce an increase in the expulsion ra

  7. Immunotoxicity of trenbolone acetate in Japanese quail

    Science.gov (United States)

    Quinn, M.J.; McKernan, M.; Lavoie, E.T.; Ottinger, M.A.

    2007-01-01

    Trenbolone acetate is a synthetic androgen that is currently used as a growth promoter in many meat-exporting countries. Despite industry laboratories classifying trenbolone as nonteratogenic, data showed that embryonic exposure to this androgenic chemical altered development of the immune system in Japanese quail. Trenbolone is lipophilic, persistent, and released into the environment in manure used as soil fertilizer. This is the first study to date to assess this chemical's immunotoxic effects in an avian species. A one-time injection of trenbolone into yolks was administered to mimic maternal deposition, and subsequent effects on the development and function of the immune system were determined in chicks and adults. Development of the bursa of Fabricius, an organ responsible for development of the humoral arm of the immune system, was disrupted, as indicated by lower masse, and smaller and fewer follicles at day 1 of hatch. Morphological differences in the bursas persisted in adults, although no differences in either two measures of immune function were observed. Total numbers of circulating leukocytes were reduced and heterophil-lymphocyte ratios were elevated in chicks but not adults. This study shows that trenbolone acetate is teratogenic and immunotoxic in Japanese quail, and provides evidence that the quail immune system may be fairly resilient to embryonic endocrine-disrupting chemical-induced alterations following no further exposure posthatch.

  8. Six new coordination polymers constructed by 3-carboxyl-5-oxycarboxymethylpyridinio-1-carboxylate: Crystal structures, topologies, photoluminescent and magnetic properties

    International Nuclear Information System (INIS)

    Six new two-dimensional (2D) coordination polymers, [ML(H2O)3]n (M=Zn (1), Cd (2), Mn (3), Co (4)), [CdL(H2O)]n (5), [CdL(4,4′-bipy)]n·nH2O (6), (H2L=3-carboxyl-5-oxycarboxymethylpyridinio-1-carboxylate, 4,4′-bipy=4,4′-bipyridine), have been hydrothermally synthesized and characterized by single crystal X-ray diffraction analyses, IR spectra, and thermogravimetric analyses. 1, 2, 3, 4 are isostructural and feature a binodal (4,6)-connected topology with left- and right-handed helical chains with a pitch of 9.9560 Å. 5 can be topologically presented as an uninodal 6-connected network if the hydrogen bonds are also considered. 6 is a binodal (3,5)-connected 2D layer network. The photoluminescent properties of 1, 2, 5, 6 and magnetic properties of 3, 4 have been studied and discussed. - Graphical abstract: The structural differences show that the ligand, the metal center, and the reaction conditions have great influence on the structure of the final assembly. - Highlights: • A new asymmetric flexible tricarboxylate ligand of 3-carboxyl-5-oxycarboxymethylpyridinio-1-carboxylate was synthesized. • Six new two-dimensional (2D) coordination polymers have been hydrothermally obtained. • 1, 2, 3, 4 are isostructural and feature a binodal (4,6)-connected topology with left- and right-handed helical chains. • The photoluminescent properties of 1, 2, 5, 6 and magnetic properties of 3, 4 have been studied

  9. Unimolecular decomposition of formic and acetic acids: A shock tube/laser absorption study

    KAUST Repository

    Elwardany, A.

    2014-07-16

    The thermal decomposition of formic acid (HCOOH) and acetic acid (CH3COOH), two carboxylic acids which play an important role in oxygenate combustion chemistry, were investigated behind reflected shock waves using laser absorption. The rate constants of the primary decomposition pathways of these acids:(HCOOH → CO + H2 O (R 1); HCOOH → CO2 + H2 (R 2); CH3 COOH → CH4 + CO2 (R 3); CH3 COOH → CH2 CO + H2 O (R 4)) were measured using simultaneous infrared laser absorption of CO, CO2 and H2O at wavelengths of 4.56, 4.18 and 2.93 microns, respectively. Reaction test conditions covered temperatures from 1230 to 1821 K and pressures from 1.0 to 6.5 atm for dilute mixtures of acids (0.25-0.6%) in argon. The rate constants of dehydration (R1) and decarboxylation (R2) reactions of formic acid were calculated by fitting exponential functions to the measured CO, CO2 and H2O time-history profiles. These two decomposition channels were found to be in the fall-off region and have a branching ratio, k1/k2, of approximately 20 over the range of pressures studied here. The best-fit Arrhenius expressions of the first-order rates of R1 and R2 were found to be:(k1 (1 atm) = 1.03 × 1011 exp (- 25651 / T) s- 1 (± 37 %); k1 (6.5 atm) = 9.12 × 1012 exp (- 30275 / T) s- 1 (± 32 %); k2 (1 atm) = 1.79 × 108 exp (- 21133 / T) s- 1 (± 41 %); k2 (6.5 atm) = 2.73 × 108 exp (- 20074 / T) s- 1 (± 37 %)). The rate constants for acetic acid decomposition were obtained by fitting simulated profiles, using an acetic acid pyrolysis mechanism, to the measured species time-histories. The branching ratio, k4/k3, was found to be approximately 2. The decarboxylation and dehydration reactions of acetic acid appear to be in the falloff region over the tested pressure range:(k3 (1 atm) = 3.18 × 1011 exp (- 28679 / T) s- 1 (± 30 %); k3 (6 atm) = 3.51 × 1012 exp (- 31330 / T) s- 1 (± 26 %); k4 (1 atm) = 7.9 × 1011 exp (- 29056 / T) s- 1 (± 34 %); k4 (6 atm) = 6.34 × 1012 exp (- 31330 / T) s

  10. Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: Thermal and mechanical properties

    Directory of Open Access Journals (Sweden)

    H. F. Xie

    2012-09-01

    Full Text Available Carboxyl-modified multi-walled carbon nanotubes (MWCNT–COOHs as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA toughened with carboxyl-terminated butadiene-acrylonitrile (CTBN. The carboxyl functional carbon nanotubes were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. Furthermore, cure kinetics, glass transition temperature (Tg, mechanical properties, thermal stability and morphology of DGEBA/CTBN/MWCNT–COOHs nanocomposites were investigated by differential scanning calorimetry (DSC, dynamic mechanical analysis (DMA, universal test machine, thermogravimetric analysis and scanning electron microscopy (SEM. DSC kinetic studies showed that the addition of MWCNT–COOHs accelerated the curing reaction of the rubber-toughened epoxy resin. DMA results revealed that Tg of rubber-toughened epoxy nanocomposites lowered with MWCNT–COOH contents. The tensile strength, elongation at break, flexural strength and flexural modulus of DGEBA/CTBN/MWCNT-COOHs nanocomposites were increased at lower MWCNT-COOH concentration. A homogenous dispersion of nanocomposites at lower MWCNT–COOH concentration was observed by SEM.

  11. Effect of medroxyprogesterone acetate (Provera) on ovarian radiosensitivity

    Energy Technology Data Exchange (ETDEWEB)

    Jarrell, J.; YoungLai, E.V.; McMahon, A.; Barr, R.; O' Connell, G.; Belbec, L.

    1989-04-01

    Medroxyprogesterone acetate (Provera) is a drug that is commonly given to young women with cancer during chemotherapy and radiation to control heavy bleeding associated with anovulation. Because hypothalamic-pituitary-ovarian suppression has been associated with ovarian protection from the effects of chemotherapy and medroxyprogesterone acetate has been identified as a radiosensitizing agent, we explored the effects of medroxyprogesterone acetate on a rat model with known radiation injury characteristics. Sprague-Dawley rats were treated with medroxyprogesterone acetate or vehicle from day 22 to day 37 of life and were either irradiated or sham-irradiated on day 30 of life and then killed on day 44. Radiation with medroxyprogesterone acetate administration produced a greater loss in preantral and healthy control follicles than in control follicles. No suppression of luteinizing hormone or follicle-stimulating hormone had occurred by day 30 but ovarian glutathione content was reduced. These findings indicate that the administration of medroxyprogesterone acetate with radiotherapy may enhance ovarian injury.

  12. Specific solvation interactions of CO2 on acetate and trifluoroacetate imidazolium based ionic liquids at high pressures.

    Science.gov (United States)

    Carvalho, Pedro J; Alvarez, Víctor H; Schröder, Bernd; Gil, Ana M; Marrucho, Isabel M; Aznar, Martín; Santos, Luís M N B F; Coutinho, João A P

    2009-05-14

    New classes of acidic or basic ionic liquids (ILs) are gaining special attention, since the efficiency of many processes can be enhanced by the judicious manipulation of these properties. The absorption of sour gases can be enhanced by the basic character of the IL. The fluorination of the cation or the anion can also contribute to enhance the gas solubility. In this work these two characteristics are evaluated through the study of the gas-liquid equilibrium of two ionic liquids based on similar anions, 1-butyl-3-methylimidazolium acetate ([C4mim][Ac]) and 1-butyl-3-methylimidazolium trifluoroacetate ([C4mim][TFA]), with carbon dioxide (CO2) at temperatures up to 363 K and pressures up to 76 MPa. The data reported are shown to be thermodynamically consistent. Henry's constants estimated from the experimental data show the solubility of CO2 on the [C4mim][Ac] to be spontaneous unlike in [C4mim][TFA] due to the differences in solvation enthalpies in these systems. Ab initio calculations were performed on simple intermolecular complexes of CO2 with acetate and trifluoroacetate using MP2/6-31G(d) and the G3 and G3MP2 theoretical procedures to understand the interactions between CO2 and the anions. The theoretical study indicates that although both anions exhibit a simultaneous interaction of the two oxygen of the carboxylate group with the CO2, the acetate acts as a stronger Lewis base than the trifluoroacetate. 13C high-resolution and magic angle spinning (HRMAS) NMR spectra provide further evidence for the acid/base solvation mechanism and the stability of the acetate ion on these systems. Further similarities and differences observed between the two anions in what concerns the solvation of CO2 are discussed. PMID:19374423

  13. Engineering of Corynebacterium glutamicum to utilize methyl acetate, a potential feedstock derived by carbonylation of methanol with CO.

    Science.gov (United States)

    Choo, Seungjung; Um, Youngsoon; Han, Sung Ok; Woo, Han Min

    2016-04-20

    The possibilities to utilize one-carbon substrates (C1) like CO, methane and methanol have been explored as a cheap alternative feedstock in the biotechnology. For the first time, methyl acetate (MeOAc), which can be formed from carbonylation of methanol with CO, was demonstrated to be an alternative carbon source for the cell growth of Corynebacterium glutamicum as a model microbial cell factory. To do so, a carboxyl esterase activity was necessary to hydrolyze MeOAc to methanol and acetate. Although the wild-type has an unknown esterase activity to MeOAc, the activity was not high enough to grow from 270mM MeOAc as sole carbon source, reaching OD600 of 5.28±0.2 in 32h. Based on the literatures studied for the esterase, we chose three esterases (MekB of Pseudomonas veronii MEK700, AcmB of Gordonia sp. Strain TY-5, and Est of Pyrobaculum calidifontis VA1) and cloned into the wild-type. As a result, the recombinant C. glutamicum expressing the highly active MekB esterase (28.6±0.77U/mg protein) showed complete degradation of MeOAc and utilization of acetate, resulting in OD600 of 16.5±0.02at 24h. In addition, the recombinant strain exhibited the rapid degradation of MeOAc to methanol and acetate in 2h under anaerobic condition. Therefore, MeOAc can be used as another C1-derived carbon source in the biotechnology. PMID:26970052

  14. Synthesis, crystal structure and electrochemical and DNA binding studies of oxygen bridged-copper(II) carboxylate

    Science.gov (United States)

    Iqbal, Muhammad; Ali, Saqib; Tahir, Muhammad Nawaz; Muhammad, Niaz; Shah, Naseer Ali; Sohail, Manzar; Pandarinathan, Vedapriya

    2015-08-01

    A new binuclear O-bridged Cu(II) complex with 4-chlorophenyl acetate and 2,2‧-bipyridine has been synthesized and characterized using FT-IR, powder and single crystal XRD and electrochemical solution studies. The results revealed that the two penta-coordinated Cu(II) centers are linked by two carboxylate ligands in end-on bonding fashion. The coordination geometry is slightly distorted square pyramidal (SP) with bridging oxygen atoms occupying the apical position and other ligands lying in the equatorial plane. The striking difference in Cu-O bond distance of the bridging oxygen atom in the complex may be responsible for the SP geometry of Cu(II) ion. The complex gave rise to metal centered irreversible electro-activity where one electron Cu(II)/Cu(III) oxidation process and a single step two electron Cu(II)/Cu(0) reduction process was observed. The redox processes were found predominantly adsorption controlled. The values of diffusion coefficient and heterogeneous rate constant for oxidation process were 6.98 × 10-7 cm2 s-1 and 4.60 × 10-5 cm s-1 while the corresponding values for reduction were 5.30 × 10-8 cm2 s-1 and 5.41 × 10-6 cm s-1, respectively. The formal potential and charge transfer coefficient were also calculated. The DNA-binding ability was explored through cyclic voltammetry and UV-Visible spectroscopy. Diminution in the value of Do for oxidation indicated the binding of the complex with DNA corresponding to Kb = 8.58 × 104 M-1. UV-Visible spectroscopy yielded ε = 49 L mol-1 cm-1 and Kb = 2.96 × 104 M-1. The data of both techniques support each other. The self-induced redox activation of the complex, as indicated by cyclic voltammetry heralds its potential applications in redox catalysis and anticancer activity.

  15. Compound list: desmopressin acetate [Open TG-GATEs

    Lifescience Database Archive (English)

    Full Text Available desmopressin acetate DDAVP 00159 ftp://ftp.biosciencedbc.jp/archive/open-tggates/LA...TEST/Rat/in_vivo/Liver/Single/desmopressin_acetate.Rat.in_vivo.Liver.Single.zip ftp://ftp.biosciencedbc.jp/a...rchive/open-tggates/LATEST/Rat/in_vivo/Liver/Repeat/desmopressin_acetate.Rat.in_vivo.Liver.Repeat.zip ftp://...ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Kidney/Single/desmopressin_aceta...te.Rat.in_vivo.Kidney.Single.zip ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Kidney/Repeat/desmopressin_acetate.Rat.in_vivo.Kidney.Repeat.zip ...

  16. Crystal structure of ammonium (3,5-di­chloro­phen­oxy)acetate hemihydrate

    OpenAIRE

    Smith, Graham

    2015-01-01

    In the structure of the title hydrated salt, NH4 +·C8H5Cl2O3 −·0.5H2O, where the anion derives from (3,5-di­chloro­phen­oxy)acetic acid, the ammonium cation is involved in extensive N—H⋯O hydrogen bonding with both carboxyl­ate and ether O-atom acceptors giving sheet structures lying parallel to (100). The water mol­ecule of solvation lies on a crystallographic twofold rotation axis and is involved in intra-sheet O—H⋯Ocarboxyl­ate hydrogen-bonding inter­actions. In the anion, the oxoacetate s...

  17. A radioimmunoassay for serum medroxyprogesterone acetate.

    Science.gov (United States)

    Shrimanker, K; Saxena, B N; Fotherby, K

    1978-04-01

    When injected intramuscularly in a dose of 150 mg, Depo Provera, a microcrystalline suspension of medroxyprogesterone acetate (MPA), will provide a contraceptive effect for at least 3 months. This paper describes a sensitive radioimmunoassay for MPA which has been used in the author's laboratory for the past 2 years. MPA was converted to MPA-3-CMO and the oxime was conjugated with bovine serum albumin (BSA) by the mixed anahydride method. 4 rabbits were immunized with the antiserum. A high titre of MPA antibodies was detected 6 months after immunization. Serum from the rabbit with the highest titre of antibodies to MPA was subjected to radioimmunoassay. 7 days after the intramuscular injection of 150 mg Depo-Provera, serum levels of MPA were found in the range of 1750 to 9000 pg/ml. By 75 days, the levels had decreased to 680-2600 pg/ml. The method was found to have adequate accuracy, precision and sensitivity. PMID:661315

  18. Toxicity of algal-derived aldehydes to two invertebrate species: Do heavy metal pollutants have a synergistic effect?

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, Rebecca L. [School of Marine Science and Technology, University of Newcastle upon Tyne, Ridley Building, Claremont Road, Newcastle upon Tyne NE1 7RU (United Kingdom)]. E-mail: r.l.taylor@ncl.ac.uk; Caldwell, Gary S. [School of Marine Science and Technology, University of Newcastle upon Tyne, Ridley Building, Claremont Road, Newcastle upon Tyne NE1 7RU (United Kingdom); Bentley, Matthew G. [School of Marine Science and Technology, University of Newcastle upon Tyne, Ridley Building, Claremont Road, Newcastle upon Tyne NE1 7RU (United Kingdom)

    2005-08-15

    The recent discovery of the production of anti-proliferative aldehydes in a variety of microalgal species has lead to considerable investigation into the effects of these toxins on aquatic invertebrates. Studies have, however, rarely considered the impact pollutants may have on grazer responses to algal toxins. In this study, the acute toxicities of five aldehydes to the rotifer Brachionus plicatilis and nauplii of the brine shrimp Artemia salina are examined using immersion assays. In addition, the effect of a representative of these aldehydes in the presence of sub-lethal levels of heavy metals was examined. B. plicatilis generally showed greater sensitivity to the aldehydes than A. salina. The polyunsaturated 2-trans,4-trans-decadienal was the most toxic to both species having 24 h LD{sub 50} values of 7 and 20 {mu}M for B. plicatilis and A. salina, respectively. The remaining aldehydes had different orders of toxicity for the two species with a stronger relationship observed between mortality and aldehyde carbon-chain length for A. salina whereas B. plicatilis mortality showed a stronger dependence on the presence of carbon-carbon double bonds in the aldehydes. The presence of 1 {mu}M of copper sulphate in solutions of decadienal resulted in the reduction of the 24 h LD{sub 50} of decadienal by approximately a third for both species. 1 {mu}M of copper chloride in solutions of decadienal reduced the 24 h LD{sub 50} of decadienal to A. salina nauplii by approximately 11% and 1 {mu}M zinc sulphate caused a reduction of only 3%. Pre-exposure of the organisms to 1 {mu}M copper sulphate had no significant impact on their subsequent mortality in decadienal. The ecological implications and the possible mechanisms for the action of copper sulphate on the response of organisms to decadienal are discussed.

  19. Toxicity of algal-derived aldehydes to two invertebrate species: Do heavy metal pollutants have a synergistic effect?

    International Nuclear Information System (INIS)

    The recent discovery of the production of anti-proliferative aldehydes in a variety of microalgal species has lead to considerable investigation into the effects of these toxins on aquatic invertebrates. Studies have, however, rarely considered the impact pollutants may have on grazer responses to algal toxins. In this study, the acute toxicities of five aldehydes to the rotifer Brachionus plicatilis and nauplii of the brine shrimp Artemia salina are examined using immersion assays. In addition, the effect of a representative of these aldehydes in the presence of sub-lethal levels of heavy metals was examined. B. plicatilis generally showed greater sensitivity to the aldehydes than A. salina. The polyunsaturated 2-trans,4-trans-decadienal was the most toxic to both species having 24 h LD50 values of 7 and 20 μM for B. plicatilis and A. salina, respectively. The remaining aldehydes had different orders of toxicity for the two species with a stronger relationship observed between mortality and aldehyde carbon-chain length for A. salina whereas B. plicatilis mortality showed a stronger dependence on the presence of carbon-carbon double bonds in the aldehydes. The presence of 1 μM of copper sulphate in solutions of decadienal resulted in the reduction of the 24 h LD50 of decadienal by approximately a third for both species. 1 μM of copper chloride in solutions of decadienal reduced the 24 h LD50 of decadienal to A. salina nauplii by approximately 11% and 1 μM zinc sulphate caused a reduction of only 3%. Pre-exposure of the organisms to 1 μM copper sulphate had no significant impact on their subsequent mortality in decadienal. The ecological implications and the possible mechanisms for the action of copper sulphate on the response of organisms to decadienal are discussed

  20. Uranyl-organic assemblies with acetate-bearing phenyl- and cyclohexyl-based ligands

    International Nuclear Information System (INIS)

    Six novel complexes formed under hydrothermal conditions by uranyl ions with three ligands comprising a rigid phenyl- or cyclohexyl-containing platform, and two to four acetate arms have been obtained. 1,3,5-Benzene-triacetic acid (H3BTA) yielded the complex [NMe4][UO2(BTA)].H2O (1), in which the structure-directing counter-ion induces a two-dimensional, bilayer-type structure different from that previously reported, with both the tris-chelating ligand and the metal ion as trigonal nodes. Two complexes were obtained with 1,2-phenylenedioxy-diacetic acid (H2PDDA), [UO2(PDDA)(H2O)] (2) and [H2DABCO][(UO2)2(PDDA)3].1.5H2O (3). Complex 2 is a simple, ribbon-like, one-dimensional polymer, while 3 is a nano-tubular assembly built around the hydrogen-bonded, structure-directing counterions. Three complexes were obtained with trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid (H4DCTA), a polyamino-poly-carboxylic acid, with different bases, [UO2(H2DCTA)(H2O)2].H2O (4), [UO2(H2DCTA)(H2O)].1.5H2O (5), and [UO2Na(HDCTA)(H2O)] (6). The nitrogen atoms are not coordinated, both of them (4) or only one (5 and 6) being protonated, and the carboxylic/ate groups are monodentate, except for one chelating in 6 and one nonbonding in 4. These differences in bonding result in various assemblies, one-dimensional in 4 and two-dimensional in 5 and 6. The layers in 5 are strongly corrugated, with the cyclohexyl groups pointing on either side, and their packing displays oval-shaped channels, while the layers in 6 are planar, with the cyclohexyl groups located on one side, and further assembled into dimeric units by the disordered sodium ions. These are the first crystal structures of actinide ion complexes with both H2PDDA and H4DCTA. (authors)

  1. (2S,4R-4-Fluoropyrrolidinium-2-carboxylate

    Directory of Open Access Journals (Sweden)

    David B. Hobart Jr

    2012-08-01

    Full Text Available The crystal structure of the title compound, C5H8FNO2, at 100 K, displays intermolecular N—H...O hydrogen bonding between the ammonium and carboxylate groups as a result of its zwitterionic nature in the solid state. The five-membered ring adopts an envelope conformation with the C atom at the 3-position as the flap. The compound is of interest with respect to the synthesis and structural properties of synthetic collagens. The absolute structure was determined by comparison with the commercially available material.

  2. Sodium borohydride reduction of aromatic carboxylic acids via methyl esters

    Indian Academy of Sciences (India)

    Aamer Saeed; Zaman Ashraf

    2006-09-01

    A number of important aromatic carboxylic acids precursors, or intermediates in the syntheses of natural products, are converted into methyl esters and reduced to the corresponding primary alcohols using a sodium borohydride-THF-methanol system. The alcohols are obtained in 70-92% yields in 2-5 hours, in a pure state. This two-step procedure not only provides a better alternative to aluminum hydride reduction of acids but also allows the selective reduction of esters in presence of acids, amides, nitriles or nitro functions which are not affected under these conditions.

  3. Synthesis and properties of scandium carboxylate metal-organic frameworks

    OpenAIRE

    Gonzalez-Santiago, Berenice

    2015-01-01

    This work investigated the synthesis, characterisation and properties of known and novel scandium carboxylate Metal-organic Frameworks (MOFs). The first part reports the performance of these Sc-MOFs as Lewis acid catalysts. The porous MOF scandium trimesate MIL-100(Sc) and the scandium terephthalates such as MIL-101(Sc), MIL-88B(Sc) and MIL-68(Sc) (prepared as the Sc-analogue for the first time), and scandium biphenyldicarboxylate MIL-88D(Sc) were prepared and tested as Lewis acid catalysts. ...

  4. Toxicity of perfluorinated carboxylic acids for aquatic organisms.

    Science.gov (United States)

    Tichý, Miloň; Valigurová, Radka; Cabala, Radomír; Uzlová, Rut; Rucki, Marián

    2010-06-01

    Toxicity of perfluorinated carboxylic acids with carbon chain C(8) to C(12) were tested with oligochaeta Tubifex tubifex. Toxicity was evaluated as the exposure time ET(50) from onset of damage of the oligochaeta in saturated aqueous solutions. The ET(50) fluctuated between 25 and 257 minutes. No statistically significant difference was found among the C(8), C(9) and C(12) acids (ET(50) between 143 and 257 minutes with large standard deviation). The acids with carbon chain C(10) and C(11) induced the effect significantly quicker (25 to 47 minutes). No acute toxicity measured in the three-minute test was observed in any case. PMID:21217876

  5. Toxicity of perfluorinated carboxylic acids for aquatic organisms

    OpenAIRE

    Tichý, Miloň; Valigurová, Radka; Čabala, Radomír; Uzlová, Rut; Rucki, Marián

    2010-01-01

    Toxicity of perfluorinated carboxylic acids with carbon chain C8 to C12 were tested with oligochaeta Tubifex tubifex. Toxicity was evaluated as the exposure time ET50 from onset of damage of the oligochaeta in saturated aqueous solutions. The ET50 fluctuated between 25 and 257 minutes. No statistically significant difference was found among the C8, C9 and C12 acids (ET50 between 143 and 257 minutes with large standard deviation). The acids with carbon chain C10 and C11 induced the effect sign...

  6. Oxidation of indole-3-acetic acid to oxindole-3-acetic acid by an enzyme preparation from Zea mays

    Science.gov (United States)

    Reinecke, D. M.; Bandurski, R. S.

    1988-01-01

    Indole-3-acetic acid is oxidized to oxindole-3-acetic acid by Zea mays tissue extracts. Shoot, root, and endosperm tissues have enzyme activities of 1 to 10 picomoles per hour per milligram protein. The enzyme is heat labile, is soluble, and requires oxygen for activity. Cofactors of mixed function oxygenase, peroxidase, and intermolecular dioxygenase are not stimulatory to enzymic activity. A heat-stable, detergent-extractable component from corn enhances enzyme activity 6- to 10-fold. This is the first demonstration of the in vitro enzymic oxidation of indole-3-acetic acid to oxindole-3-acetic acid in higher plants.

  7. Liquid-Liquid equilibria of the water-acetic acid-butyl acetate system

    Directory of Open Access Journals (Sweden)

    E. Ince

    2002-04-01

    Full Text Available Experimental liquid-liquid equilibria of the water-acetic acid-butyl acetate system were studied at temperatures of 298.15± 0.20, 303.15± 0.20 and 308.15± 0.20 K. Complete phase diagrams were obtained by determining solubility and tie-line data. The reliability of the experimental tie-line data was ascertained by using the Othmer and Tobias correlation. The UNIFAC group contribution method was used to predict the observed ternary liquid-liquid equilibrium (LLE data. It was found that UNIFAC group interaction parameters used for LLE did not provide a good prediction. Distribution coefficients and separation factors were evaluated for the immiscibility region.

  8. Different cerebrovascular effects of medroxyprogesterone acetate and norethisterone acetate in the New Zealand White rabbit

    DEFF Research Database (Denmark)

    Pedersen, S H; Pedersen, N G; Dalsgaard, T;

    2004-01-01

    overall differences were seen between CEE and E2. CONCLUSIONS: In rabbit cerebral arteries, MPA treatment causes a higher development in arterial tension compared with NETA, indicating that different progestins may display different cerebrovascular effects. However, when accompanied by estrogens, as in......OBJECTIVE: The lack of a cardioprotective effect of hormone replacement therapy (HRT), as suggested by the Heart and Estrogen/progestin Replacement Study (HERS) and Women's Health Initiative (WHI) may in part be explained by the progestin used. The aim of this study was to elucidate the effect of...... different progestins on cerebrovascular reactivity in an animal model. METHODS: Fifty-six ovariectomized New Zealand White rabbits were randomized into seven groups receiving hormone treatment for 4 weeks: medroxyprogesterone acetate (MPA) (10 mg/day); norethisterone acetate (NETA) (3 mg/day); conjugated...

  9. EFFECT OF DIFFERENT TREATMENTS ON CELLULOSE TOWARD CARBOXYLATION AND ITS APPLICATION FOR METAL ION ABSORPTION

    Directory of Open Access Journals (Sweden)

    A. M. A. Nada

    2009-02-01

    Full Text Available Carboxylation of cotton linters was investigated relative to its use in ion exchange. The effects of different treatments of cotton linters, such as alkali, acid, and activating agents, e.g. LiCl, on the molecular structure and carboxylation of cotton linters were taken in our consideration. The absence or presence of a crosslinking was considered, and the efficiency of these prepared carboxylated cotton linters toward metal ions uptake, as well as thermal analysis of treated and carboxylated cotton linters, was investigated. It was found that treatment of cotton linters with alkali and activating agent decreased the crystallinity index (band intensity at 1425/band intensity at 890 cm-1. On the other hand, the prepared carboxylated cotton linters had lower crystallinity index than uncarboxylated linters. Thermal analysis of the treated and carboxylated cotton linters allowed calculation of the activation energy of thermally treated materials. It was found that the crosslinked and acid treated cotton linters had a higher activation.

  10. Integrated quantification and identification of aldehydes and ketones in biological samples.

    Science.gov (United States)

    Siegel, David; Meinema, Anne C; Permentier, Hjalmar; Hopfgartner, Gérard; Bischoff, Rainer

    2014-05-20

    The identification of unknown compounds remains to be a bottleneck of mass spectrometry (MS)-based metabolomics screening experiments. Here, we present a novel approach which facilitates the identification and quantification of analytes containing aldehyde and ketone groups in biological samples by adding chemical information to MS data. Our strategy is based on rapid autosampler-in-needle-derivatization with p-toluenesulfonylhydrazine (TSH). The resulting TSH-hydrazones are separated by ultrahigh-performance liquid chromatography (UHPLC) and detected by electrospray ionization-quadrupole-time-of-flight (ESI-QqTOF) mass spectrometry using a SWATH (Sequential Window Acquisition of all Theoretical Fragment-Ion Spectra) data-independent high-resolution mass spectrometry (HR-MS) approach. Derivatization makes small, poorly ionizable or retained analytes amenable to reversed phase chromatography and electrospray ionization in both polarities. Negatively charged TSH-hydrazone ions furthermore show a simple and predictable fragmentation pattern upon collision induced dissociation, which enables the chemo-selective screening for unknown aldehydes and ketones via a signature fragment ion (m/z 155.0172). By means of SWATH, targeted and nontargeted application scenarios of the suggested derivatization route are enabled in the frame of a single UHPLC-ESI-QqTOF-HR-MS workflow. The method's ability to simultaneously quantify and identify molecules containing aldehyde and ketone groups is demonstrated using 61 target analytes from various compound classes and a (13)C labeled yeast matrix. The identification of unknowns in biological samples is detailed using the example of indole-3-acetaldehyde. PMID:24745975

  11. The effects of using oxygenated fuels on the concentrations of Aldehydes in Denver

    International Nuclear Information System (INIS)

    The State of Colorado has mandated the winter use of oxygenated fuels in motor vehicles since January 1988. The purpose of using oxygenated fuels is to reduce the emissions of carbon monoxide (CO), and hence the ambient concentration of carbon monoxide. The use of oxygenated fuels is known to increase the emissions of aldehydes. Formaldehyde emissions increase when methyl tertiary butyl ether (MTBE) blended fuels are used, while acetaldehyde emissions also increase when ethanol blended fuels are used. Early in the program, MTBE blended fuels constituted about 95% of the fuels used. The market penetration of the ethanol blended fuels is believed to have increased to about 20% in recent years. Our research group has been collecting four-hour averaged aldehyde samples, 24 hours a day in Denver for much of the time since December 1987. This has included six seasons during which oxygenated fuels were used. In this paper, the diurnal and seasonal variability in the aldehyde concentrations are discussed. These data suggest that motor vehicles are a major source of formaldehyde during the winter. Other sources of formaldehyde, including photochemical sources, are of greater importance during the summer. These data will be analyzed to try to evaluate the impact of using oxygenated fuels on the atmospheric concentration of formaldehyde in Denver. The 1990 Clean Air requires the use of oxygenated fuels in over forty metropolitan areas with carbon monoxide problems. It must be verified that one is not causing new problems by the use of oxygenated fuels in an attempt to reduce carbon monoxide concentrations

  12. Inhibition of guinea pig aldehyde oxidase activity by different flavonoid compounds: An in vitro study.

    Science.gov (United States)

    Siah, Maryam; Farzaei, Mohammad Hosein; Ashrafi-Kooshk, Mohammad Reza; Adibi, Hadi; Arab, Seyed Shahriar; Rashidi, Mohammad Reza; Khodarahmi, Reza

    2016-02-01

    Aldehyde oxidase (AO), a cytosolic molybdenum-containing hydroxylase, is predominantly active in liver and other tissues of mammalian species and involved in the metabolism of extensive range of aldehydes and nitrogen-containing compounds. A wide range of natural components including polyphenols are able to interfere with AO-catalyzed reactions. Polyphenols and flavonoids are one of the extensive secondary plant metabolites ubiquitously present in plants considered an important part of the human diet. The aim of the present study was to investigate inhibitory effect of selected phenolic compounds from three subclasses of aurone, flavanone and phenolic lactone compounds on the activity of AO, spectrophotometrically. AO enzyme was partially purified from liver of guinea pig. Then, inhibitory effects of 10 flavonoid compounds including 8 derivatives of 2-benzylidenebenzofuran-3(2H)-ones, as well as naringenin and ellagic acid on the activity of aldehyde oxidase were assessed compared with the specific inhibitor of AO, menadione. Among the phenolic compounds with inhibitory effects on the enzyme, ellagic acid (IC50=14.47μM) was the most potent agent with higher inhibitory action than menadione (IC50=31.84μM). The mechanisms by which flavonoid compounds inhibit AO activity have been also determined. The inhibitory process of the assessed compounds occurs via either a non-competitive or mixed mode. Although flavonoid compounds extensively present in the nature, mainly in dietary regimen, aurones with promising biological properties are not widely distributed in nature, so synthesis of aurone derivatives is of great importance. Additionally, aurones seem to provide a promising scaffold in medicinal chemistry for the skeleton of new developing drugs, so the results of the current study can be valuable in order to better understanding drug-food as well as drug-drug interaction and also appears to be worthwhile in drug development strategies. PMID:26722818

  13. Electrochemical deposition of a copper carboxylate layer on copper as potential corrosion inhibitor

    OpenAIRE

    Elia, Alice; De Wael, Karolien; Dowsett, Mark; Adriaens, Annemie

    2012-01-01

    Carboxylic acids and sodium carboxylates are used to protect metals against aqueous and atmospheric corrosion. In this paper we describe the application of a layer of copper carboxylate on the surface of a copper electrode by means of cyclic voltammetry technique, and tests which measure the corresponding resistance to aqueous corrosion. Unlike the soaking process, which also forms a film on the surface, the use of cyclic voltammetry allows one to follow the deposition process of the copper c...

  14. A synthetic approach to carbon-14 labeled anti-bacterial naphthyridine and quinolone carboxylic acids

    Energy Technology Data Exchange (ETDEWEB)

    Ekhato, I.V.; Huang, C.C. (Parke, Davis and Co., Ann Arbor, MI (United States))

    1993-09-01

    Labeled versions of (S)-clinafloxacin (1) and two napththyridine carboxylic acid anti-bacterial compounds 2 and 3 which are currently in development were synthesized. Preparations started from hitherto unknown bromo compounds 22 and 10, from which the corresponding [sup 14]C-labeled aromatic carboxylic acids 23 and 12 were generated by metal-halogen exchange followed by carboxylation reaction. Details of these preparations are given. (author).

  15. Clean Synthesis in Water:Darzens Condensation Reaction of Aromatic Aldehydes with Phenacyl Chloride

    Institute of Scientific and Technical Information of China (English)

    史达清; 张姝; 庄启亚; 王香善; 屠树江; 胡宏纹

    2003-01-01

    The Darzens condensation reaction of aromatic aldehydes with phenacyl chloride proceeded very efficiently in a water suspension medium in the presence of triethylbenzylammonium chloride and only trans-2,3-epoxy-1,3-diaryl-1-propanones were formed which can be isolated simply by filtration.The structures of these compounds were confirmed by elemental analysis,IR and 1H NMR spectra.Therir configurations are in agreement with that of the same compounds reported in the literature.Compared to the classical Darzens condensation,this new method has the advantages of good yields,high stereoselectivity,low running cost inexpensive and environmentally benign procedure.

  16. From ribonucleoside 5'-aldehydes to ribonucleoside 5'-C-phosphpnates as building blocks for oligonucleotide synthesis

    Czech Academy of Sciences Publication Activity Database

    Petrová, Magdalena; Králíková, Šárka; Buděšínský, Miloš; Rosenberg, Ivan

    -, č. 52 (2008), s. 591-592. ISSN 0261-3166. [Joint Symposium of the International Roundtable on Nucleosides, Nucleotides and Nucleic Acids /18./ and the International Symposium on Nucleic Acid Chemistry /35./. Kyoto, 08.09.2008-12.09.2008] R&D Projects: GA MŠk(CZ) LC06061; GA MŠk(CZ) LC06077 Grant ostatní: EMIL-FP6(XE) 503569 Institutional research plan: CEZ:AV0Z40550506 Keywords : 5'-aldehydes * 5'-C-phosphonates Subject RIV: CC - Organic Chemistry

  17. Photocycloaddition of aromatic and aliphatic aldehydes to isoxazoles: Cycloaddition reactivity and stability studies

    Directory of Open Access Journals (Sweden)

    Hidehiro Kotaka

    2011-01-01

    Full Text Available The first photocycloadditions of aromatic and aliphatic aldehydes to methylated isoxazoles are reported. The reactions lead solely to the exo-adducts with high regio- and diastereoselectivities. Ring methylation of the isoxazole substrates is crucial for high conversions and product stability. The 6-arylated bicyclic oxetanes 9a–9c were characterized by X-ray structure analyses and showed the highest thermal stabilities. All oxetanes formed from isoxazoles were highly acid-sensitive and also thermally unstable. Cleavage to the original substrates is dominant and the isoxazole derived oxetanes show type T photochromism.

  18. Benzazole derivatives. IV. Reaction of 1,2,3-trimethylbenzimidazolium salts with aromatic aldehydes

    Directory of Open Access Journals (Sweden)

    CORINA CERNATESCU

    2005-12-01

    Full Text Available 1,2,3-Trimethylbenzimidazolium iodide and its analogue salts with one or two substituents on benzene ring (X = NO2, Br,Cl, CH3 are, due to the reactivity of the 2-methyl group, able to react with para-substituted aromatic aldehydes (X = OH, OCH3, CH3, NMe2, NO2 using piperidine as a catalyst. 1-Methyl-2-styrylbenzimidazole iodomethylates were obtained and their structure elucidated by means of NMR and IR spectroscopy. The compounds are interesting as hemicyanine dyes. They lend themselves to studies based on electronic absorption spectroscopy and they have potential practical applications linked to their photosensitive properties.

  19. Fluorescence method for enzyme analysis which couples aromatic amines with aromatic aldehydes

    Science.gov (United States)

    Smith, R.E.; Dolbeare, F.A.

    1980-10-21

    Analysis of proteinases is accomplished using conventional amino acid containing aromatic amine substrates. Aromatic amines such as 4-methoxy-2-naphthylamine (4M2NA), 2-naphthylamine, aminoisophthalic acid dimethyl ester, p-nitroaniline, 4-methoxy-1-aminofluorene and coumarin derivatives resulting from enzymatic hydrolysis of the substrate couples with aromatic aldehydes such as 5-nitrosalicylaldehyde (5-NSA), benzaldehyde and p-nitrobenzaldehyde to produce Schiff-base complexes which are water insoluble. Certain Schiff-base complexes produce a shift from blue to orange-red (visible) fluorescence. Such complexes are useful in the assay of enzymes. No Drawings

  20. Aldehyde Dehydrogenase 2 Knockout Accentuates Ethanol-Induced Cardiac Depression: Role of Protein Phosphatases

    OpenAIRE

    Ma, Heng; Byra, Emily A.; Yu, Lu; Hu, Nan; Kitagawa, Kyoko; Nakayama, Keiichi I.; Kawamoto, Toshihiro; Ren, Jun

    2010-01-01

    Alcohol consumption leads to myocardial contractile dysfunction possibly due to the toxicity of ethanol and its major metabolite acetaldehyde. This study was designed to examine the influence of mitochondrial aldehyde dehydrogenase-2 (ALDH2) knockout (KO) on acute ethanol exposure-induced cardiomyocyte dysfunction. Wild-type (WT) and ALDH2 KO mice were subjected to acute ethanol (3 g/kg, i.p.) challenge and cardiomyocyte contractile function was assessed 24 hrs later using an IonOptix® edge-d...