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Sample records for aliphatic monocarboxylic acids

  1. Effect of aliphatic, monocarboxylic, dicarboxylic, heterocyclic and sulphur-containing amino acids on Leishmania spp. chemotaxis.

    PubMed

    Diaz, E; Zacarias, A K; Pérez, S; Vanegas, O; Köhidai, L; Padrón-Nieves, M; Ponte-Sucre, A

    2015-11-01

    In the sand-fly mid gut, Leishmania promastigotes are exposed to acute changes in nutrients, e.g. amino acids (AAs). These metabolites are the main energy sources for the parasite, crucial for its differentiation and motility. We analysed the migratory behaviour and morphological changes produced by aliphatic, monocarboxylic, dicarboxylic, heterocyclic and sulphur-containing AAs in Leishmania amazonensis and Leishmania braziliensis and demonstrated that L-methionine (10-12 m), L-tryptophan (10-11 m), L-glutamine and L-glutamic acid (10-6 m), induced positive chemotactic responses, while L-alanine (10-7 m), L-methionine (10-11 and 10-7 m), L-tryptophan (10-11 m), L-glutamine (10-12 m) and L-glutamic acid (10-9 m) induced negative chemotactic responses. L-proline and L-cysteine did not change the migratory potential of Leishmania. The flagellum length of L. braziliensis, but not of L. amazonensis, decreased when incubated in hyperosmotic conditions. However, chemo-repellent concentrations of L-alanine (Hypo-/hyper-osmotic conditions) and L-glutamic acid (hypo-osmotic conditions) decreased L. braziliensis flagellum length and L-methionine (10-11 m, hypo-/hyper-osmotic conditions) decreased L. amazonensis flagellum length. This chemotactic responsiveness suggests that Leishmania discriminate between slight concentration differences of small and structurally closely related molecules and indicates that besides their metabolic effects, AAs play key roles linked to sensory mechanisms that might determine the parasite's behaviour.

  2. Induction of human choriogonadotropin in HeLa-cell cultures by aliphatic monocarboxylates and inhibitors of deoxyribonucleic acid synthesis

    PubMed Central

    Ghosh, Nimai K.; Rukenstein, Adriana; Cox, Rody P.

    1977-01-01

    The ectopic production of the glycopeptide hormone human placental choriogonadotropin by HeLa65 cells was measured by radioimmunoassay with antiserum against the β-subunit of choriogonadotropin and with the 125I-labelled β-subunit as a tracer antigen. Choriogonadotropin synthesis was markedly (500-fold) stimulated by sodium butyrate. Kinetic studies and the use of an inhibitor of protein synthesis, cycloheximide, indicated that protein synthesis was required for this induction. Investigation of the efficiency of 22 aliphatic short-chain fatty acids and derivatives in causing increased choriogonadotropin synthesis by HeLa cells showed stringent structural requirements. Induction of choriogonadotropin synthesis in HeLa cells was not restricted to butyrate. Other aliphatic acids (propionate, isobutyrate, valerate and hexanoate) were also capable of inducing choriogonadotropin synthesis at 10–50% of the efficiency of butyrate. Hydroxy derivatives of monocarboxylate inducers, related mono- and di-carboxylic acids, alcohols, amines, ketones, esters and sulphoxide were ineffective in increasing choriogonadotropin production by HeLa cells. A saturated C4 straight-chain acid without substituent hydroxyl groups but with a methyl group at one end and a carboxyl moiety at the other appeared to be most efficient in activating choriogonadotropin production. A second clonal line of HeLa cells, HeLa71, showed a higher constitutive synthesis of choriogonadotropin than HeLa65 cells, which was also markedly increased by butyrate. Butyrate and other aliphatic monocarboxylate inducers of choriogonadotropin synthesis inhibited HeLa-cell growth and DNA synthesis. This inhibition of DNA replication may be related to the mechanism of choriogonadotropin synthesis, since two well-characterized anti-neoplastic inhibitors of DNA synthesis, hydroxyurea and 1-β-d-arabinofuranosylcytosine, also stimulated a 300-fold increase in choriogonadotropin synthesis in HeLa cells and were synergistic

  3. Synthesis of higher monocarboxylic acids

    SciTech Connect

    Taikov, B.F.; Novakovskii, E.M.; Zhelkovskaya, V.P.; Shadrova, V.N.; Shcherbik, P.K.

    1981-01-01

    Brown-coal and peat waxes contain higher monocarboxylic acids, alcohols and esters of them as their main components. In view of this, considerable interest is presented by the preparation of individual compounds among those mentioned above, which is particularly important in the study of the composition and development of the optimum variants of the chemical processing of the waxes. In laboratory practice, to obtain higher monocarboxylic acids use is generally made of electrosynthesis according to Kolbe which permits unbranched higher aliphatic acids with given lengths of the hydrocarbon chain to be obtained. The aim of the present work was to synthesize higher monocarboxylic acids: arachidic, behenic, lignoceric, pentacosanoic, erotic, heptacosanoic, montanic, nonacosanoic, melissic, dotriacontanoic and tetratriacontanoic, which are present in waxes. Characteristics of synthesized acids are tabulated. 20 refs.

  4. Quantification of monocarboxylic acids in the Murchison carbonaceous meteorite

    NASA Technical Reports Server (NTRS)

    Lawless, J. G.; Yuen, G. U.

    1979-01-01

    The abundances of some of the straight- and branched-chain isomers of the monocarboxylic acids found in the Murchison carbonaceous chondrite are determined. Monocarboxylic acids extracted from a crushed sample of Murchison interior were quantified by means of gas chromatography and mass spectroscopy after a spiking solution of deuterated analogues of 11 carboxylic acids had been added. Monocarboxylic acid abundances are found to range between 1.83 and 0.01 micromole/g, which is significantly higher than Murchison amino acid concentrations, and to decrease with increasing carbon number for both branched and unbranched molecules. The results are interpreted to support the abiotic extraterrestrial synthesis of monocarboxylic acids. Possible mechanisms leading to the equal synthesis of branched and each unbranched carboxylic acid with the same carbon number are considered, noting that the Fischer-Tropsch Type mechanism by itself is incapable of accounting for the observed distributions.

  5. Isotopic and molecular analyses of hydrocarbons and monocarboxylic acids of the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Krishnamurthy, R. V.; Epstein, S.; Cronin, John R.; Pizzarello, Sandra; Yuen, George U.

    1992-01-01

    The monocarboxylic acids and hydrocarbons of the Murchison meteorite (CM2) were isolated for isotropic analysis. The nonvolatile hydrocarbons were analyzed as crude methanol and benzene-methanol extracts and also after separation by silica gel chromatography into predominantly aliphatic, aromatic, and polar hydrocarbon fractions. The volatile hydrocarbons were obtained after progressive decomposition of the meteorite matrix by freeze-thaw, hot water, and acid treatment. Molecular analyses of the aromatic hydrocarbons showed them to comprise a complex suite of compounds in which pyrene, fluoranthene, phenanthrene, and acenaphthene were the most abundant components, a result similar to earlier analyses. The polar hydrocarbons also comprise a very complex mixture in which aromatic ketones, nitrogen, and sulfur heterocycles were identified. The monocarboxylic acids, aliphatic, aromatic, and polar hydrocarbons, and the indigenous volatile hydrocarbons were found to be D-rich. The deuterium enrichment observed in these compounds is suggestive. In two separate analyses, the delta-D values of the nonvolatile hydrocarbons were observed to increase in the following order: aliphatic-aromatic-polar. This finding is consistent with an early solar system or parent body conversion of aromatic to aliphatic compounds as well as the suggestion of pyrolytic formation of aromatic from aliphatic compounds.

  6. Temporary protection of metals against atmospheric corrosion by saturated straight chain aliphatic monocarboxylates. Mechanisms of inhibition

    SciTech Connect

    Kapin, C.; Steinmetz, P.; Steinmetz, J.

    1998-12-31

    This work was devoted to the investigations of the ability of saturated straight chain aliphatic monocarboxylates to inhibit corrosion of mild steel and zinc in aerated aqueous solutions. Performances of inhibitors were shown to be dependent on their chain length, their concentration and the immersion duration. Both crystallographic parameters and solubilities of iron and zinc carboxylates were determined. Then potential-pH diagrams of iron and zinc in water were built taking the presence of metallic soaps into account. According to these diagrams, the passivation of metals was attributed to the growth of films containing metallic soaps. This model confirms that previously proposed for inhibition of copper and magnesium by the same carboxylates.

  7. Chirality of meteoritic free and IOM-derived monocarboxylic acids and implications for prebiotic organic synthesis

    NASA Astrophysics Data System (ADS)

    Aponte, José C.; Tarozo, Rafael; Alexandre, Marcelo R.; Alexander, Conel M. O.'D.; Charnley, Steven B.; Hallmann, Christian; Summons, Roger E.; Huang, Yongsong

    2014-04-01

    The origin of homochirality and its role in the development of life on Earth are among the most intriguing questions in science. It has been suggested that carbonaceous chondrites seeded primitive Earth with the initial organic compounds necessary for the origin of life. One of the strongest pieces of evidence supporting this theory is that certain amino acids in carbonaceous chondrites display a significant L-enantiomeric excess (ee), similar to those use by terrestrial life. Analyses of ee in meteoritic molecules other than amino acids would shed more light on the origins of homochirality. In this study we investigated the stereochemistry of two groups of compounds: (1) free monocarboxylic acids (MCAs) from CM2 meteorites LON 94101 and Murchison; and (2) the aliphatic side chains present in the insoluble organic matter (IOM) and extracted in the form of monocarboxylic acids (MCAs) from EET 87770 (CR2) and Orgueil (CI1). Contrary to the well-known ee observed for amino acids in meteorites, we found that meteoritic branched free and IOM-derived MCAs with 5-8 carbon atoms are essentially racemic. The racemic nature of these compounds is used to discuss the possible influence of ultraviolet circularly polarized light (UVCPL) and aqueous alterations on the parent body on chirality observed in in carbonaceous chondrites.

  8. Combinatorics of aliphatic amino acids.

    PubMed

    Grützmann, Konrad; Böcker, Sebastian; Schuster, Stefan

    2011-01-01

    This study combines biology and mathematics, showing that a relatively simple question from molecular biology can lead to complicated mathematics. The question is how to calculate the number of theoretically possible aliphatic amino acids as a function of the number of carbon atoms in the side chain. The presented calculation is based on earlier results from theoretical chemistry concerning alkyl compounds. Mathematical properties of this number series are highlighted. We discuss which of the theoretically possible structures really occur in living organisms, such as leucine and isoleucine with a chain length of four. This is done both for a strict definition of aliphatic amino acids only involving carbon and hydrogen atoms in their side chain and for a less strict definition allowing sulphur, nitrogen and oxygen atoms. While the main focus is on proteinogenic amino acids, we also give several examples of non-proteinogenic aliphatic amino acids, playing a role, for instance, in signalling. The results are in agreement with a general phenomenon found in biology: Usually, only a small number of molecules are chosen as building blocks to assemble an inconceivable number of different macromolecules as proteins. Thus, natural biological complexity arises from the multifarious combination of building blocks.

  9. Quantification of monocarboxylic acids from a spark discharge synthesis. [in meteorites

    NASA Technical Reports Server (NTRS)

    Yuen, G. U.; Lawless, J. G.; Edelson, E. H.

    1981-01-01

    A suite of sixteen monocarboxylic acids having carbon numbers 2 to 7, formed by the Miller-Urey spark discharge process, was identified and quantified by gas chromatography and mass fragmentography using a deuterium spiking technique. The molar concentration and isomeric distribution of these laboratory synthesized monocarboxylic acids are compared to those previously reported for the Murchison meteorite. They show similar trends, namely, decreasing molar concentration with increasing molecular weight, and a ratio of normal/branched isomers tending toward smaller values with increasing carbon numbers.

  10. Transepithelial transport of ferulic acid by monocarboxylic acid transporter in Caco-2 cell monolayers.

    PubMed

    Konishi, Yutaka; Shimizu, Makoto

    2003-04-01

    Our previous study (Biosci. Biotechnol. Biochem., 66, 2449-2457 (2002)), suggested that ferulic acid was transported via a monocarboxylic acid transporter (MCT). Transepithelial transport of ferulic acid was examined in this study by directly measuring the rate of its transport across Caco-2 cell monolayers. Ferulic acid transport was dependent on pH, and in a vectorical way in the apical-basolateral direction. The permeation of ferulic acid was concentration-dependent and saturable; the Michaelis constant was 16.2 mM and the maximum velocity was 220.4 nmol min-1 (mg protein)-1. Various substrates for MCTs, such as benzoic acid and acetic acid, strongly inhibited the permeation of ferulic acid, demonstrating that ferulic acid is obviously transported by MCT. Antioxidative phenolic acid compounds from dietary sources like ferulic acid would be recognized and transported by MCT by intestinal absorption.

  11. Increase in the permeability of tonoplast of garlic (Allium sativum) by monocarboxylic acids.

    PubMed

    Bai, Bing; Li, Lei; Hu, Xiaosong; Wang, Zhengfu; Zhao, Guanghua

    2006-10-18

    Immersion of intact aged garlic (Allium sativum) cloves in a series of 5% weak organic monocarboxylate solutions (pH 2.0) resulted in green color formation. No color was formed upon treatment with other weak organic acids, such as citric and malic acids, and the inorganic hydrochloric acid under the same conditions. To understand the significance of monocarboxylic acids and their differing function from that of other acids, acetic acid was compared with organic acids citric and malic and the inorganic hydrochloric acid. The effects of these acids on the permeability of plasma and intracellular membrane of garlic cells were measured by conductivity, light microscopy, and transmission electron microscopy. Except for hydrochloric acid, treatment of garlic with all three organic acids greatly increased the relative conductivity of their respective pickling solutions, indicating that all tested organic acids increased the permeability of plasma membrane. Moreover, a pickling solution containing acetic acid exhibited 1.5-fold higher relative conductivity (approximately 90%) as compared to those (approximately 60%) of both citric and malic acids, implying that exposure of garlic cloves to acetic acid not only changed the permeability of the plasma membrane but also increased the permeability of intracellular membrane. Exposure of garlic to acetic acid led to the production of precipitate along the tonoplast, but no precipitate was formed by citric and malic acids. This indicates that the structure of the tonoplast was damaged by this treatment. Further support for this conclusion comes from results showing that the concentration of thiosulfinates [which are produced only by catalytic conversion of S-alk(en)yl-l-cysteine sulfoxides in cytosol by alliinase located in the vacuole] in the acetic acid pickling solution is 1.3 mg/mL, but almost no thiosulfinates were detected in the pickling solution of citric and malic acids. Thus, all present results suggest that damage of

  12. 40 CFR 721.2270 - Aliphatic dicarboxylic acid salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Aliphatic dicarboxylic acid salt. 721... Substances § 721.2270 Aliphatic dicarboxylic acid salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as aliphatic dicarboxylic...

  13. 40 CFR 721.2270 - Aliphatic dicarboxylic acid salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Aliphatic dicarboxylic acid salt. 721... Substances § 721.2270 Aliphatic dicarboxylic acid salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as aliphatic dicarboxylic...

  14. 40 CFR 721.2270 - Aliphatic dicarboxylic acid salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aliphatic dicarboxylic acid salt. 721... Substances § 721.2270 Aliphatic dicarboxylic acid salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as aliphatic dicarboxylic...

  15. 40 CFR 721.2270 - Aliphatic dicarboxylic acid salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Aliphatic dicarboxylic acid salt. 721... Substances § 721.2270 Aliphatic dicarboxylic acid salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as aliphatic dicarboxylic...

  16. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting...

  17. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting...

  18. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting...

  19. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting...

  20. 40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.6140 Dialkyldithiophosphoric acid, aliphatic amine salt. (a) Chemical... as a dialkyldithiophosphoric acid, aliphatic amine salt (P-90-1839) is subject to reporting...

  1. 40 CFR 721.2270 - Aliphatic dicarboxylic acid salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic dicarboxylic acid salt. 721... Substances § 721.2270 Aliphatic dicarboxylic acid salt. (a) Chemical substance and significant new uses... salt (PMN P-92-1352) is subject to reporting under this section for the significant new uses...

  2. Carbon isotope composition of low molecular weight hydrocarbons and monocarboxylic acids from Murchison meteorite

    NASA Astrophysics Data System (ADS)

    Yuen, G.; Blair, N.; Des Marais, D. J.; Chang, S.

    1984-01-01

    Carbon isotopic compositions have been measured for individual hydrocarbons and monocarboxylic acids from the Murchison meteorite, a C2 carbonaceous chondrite which fell in Australia in 1969. With few exceptions, notably benzene, the volatile products are substantially isotopically heavier than their terrestrial counterparts, signifying their extraterrestrial origin. For both classes of compounds, the ratio of C-13 to C-12 decreases with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic ratio than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with the kinetically controlled synthesis of higher homologues from lower ones. The results suggest the possibility that the production mechanisms for hydrocarbons and carboxylic acids may be similar, and impose constraints on the identity of the reactant species.

  3. Role of palladium in the redox electrochemistry of ferrocene monocarboxylic acid encapsulated within ORMOSIL networks.

    PubMed

    Pandey, P C; Upadhyay, B C

    2005-07-14

    We report herein the effect of palladium on the redox electrochemistry of ferrocene monocarboxylic acid encapsulated within an organically modified sol-gel glass network (ORMOSIL). It has been found that amount of palladium and its geometrical distribution significantly alter the redox electrochemistry of FcMCA. The geometrical distribution of palladium has been controlled by two methods: (i) palladium is allowed to link within nanostructured network of the ORMOSIL which was subsequently availed from the reactivity of palladium chloride and trimethoxysilane; (ii) palladium powder is encapsulated together FcMCA thus allowing the presence of palladium within the nanoporous domain. The content of palladium is varied by controlling the reaction dynamics of palladium chloride and trimethoxysilane interaction. For this we initially allowed to trigger hydrolysis, condensation and poly-condensation of trimethoxysilane and dimethyldiethoxysilane in acidic medium and subsequently partially dried ORMOSIL film was allowed to interact with palladium chloride. Even with partially dried ORMOSIL derived from trimethoxysilane and dimethyldiethoxysilane undergoes rapid interaction with palladium chloride and the transparent color of ORMOSIL changed to a black colour due to the formation of palladium silicon linkage. The palladium-silicon linkage has been identified by NMR, UV-VIS and transmission electron spectroscopy. The electrochemistry of FcMCA encapsulated within such an ORMOSIL matrix has been studied. Excellent redox electrochemistry of ferrocene monocarboxylic acid having peak potential separation tending to 0 for a multilayered electrode was investigated. The palladium content has been found to affect the redox electrochemistry of ferrocene as well as electrocatalytic efficiency of new ORMOSIL material. The electroanalysis of NADH is reported. The modified electrode is very sensitive to NADH with lowest detection limit of < 1 microM.

  4. Process for producing peracids from aliphatic hydroxy carboxylic acids

    DOEpatents

    Chum, H.L.; Palasz, P.D.; Ratcliff, M.A.

    1984-12-20

    A process is described for producing peracids from lactic acid-containing solutions derived from biomass processing systems. It consists of adjusting the pH of the solution to about 8 to 9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids. The solution is oxidized to produce volatile lower aliphatic aldehydes. The aldehydes are removed as they are generated and converted to peracids.

  5. Process for producing peracids from aliphatic hydroxy carboxylic acids

    DOEpatents

    Chum, Helena L.; Ratcliff, Matthew A.; Palasz, Peter D.

    1986-01-01

    A process for producing peracids from lactic acid-containing solutions derived from biomass processing systems comprising: adjusting the pH of the solution to about 8-9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids; oxidizing the solution to produce volatile lower aliphatic aldehydes; removing said aldehydes as they are generated; and converting said aldehydes to peracids.

  6. Noncovalent-bonded 1D-3D supramolecular architectures from 2-methylquinoline/quinoline with monocarboxylic acid and dicarboxylic acid

    NASA Astrophysics Data System (ADS)

    Gao, Xingjun; Jin, Shouwen; Jin, Li; Ye, XiangHang; Zheng, Lu; Li, JingWen; Jin, BinPeng; Wang, Daqi

    2014-10-01

    Studies concentrating on noncovalent weak interactions between the organic base of 2-methylquinoline/quinoline, and carboxylic acid derivatives have led to an increased understanding of the role 2-methylquinoline/quinoline have in binding with carboxylic acids. Here anhydrous multicomponent organic acid-base adducts of 2-methylquinoline/quinoline have been prepared with carboxylic acids that ranged from monocarboxylic acid to dicarboxylic acid such as p-nitrobenzoic acid, (4-chloro-phenoxy)-acetic acid, 4-hydroxy-benzoic acid, 5-bromosalicylic acid, 2,4-dihydroxybenzoic acid, α-ketoglutaric acid, and 4-nitrophthalic acid. The seven crystalline complexes were characterized by X-ray diffraction analysis, IR, m.p., and elemental analysis. These structures adopted the hetero supramolecular synthons. Analysis of the crystal packing of 1-7 suggests that there are Nsbnd H⋯O, Osbnd H⋯N, and Osbnd H⋯O hydrogen bonds (charge assisted or neutral) between the acid and quinoline moieties in the studied compounds. Except the classical hydrogen bonding interactions, the secondary propagating interactions also play important roles in structure extension. These weak interactions combined, these compounds displayed 1D-3D framework structure.

  7. On the possibility of using short chain length mono-carboxylic acids for stabilization of magnetic fluids

    NASA Astrophysics Data System (ADS)

    Avdeev, Mikhail V.; Bica, Doina; Vékás, Ladislau; Marinica, Oana; Balasoiu, Maria; Aksenov, Victor L.; Rosta, László; Garamus, Vasil M.; Schreyer, Andreas

    2007-04-01

    Short chain length mono-carboxylic acids (lauric and myristic acids) are used to coat magnetite nanoparticles in non-polar organic liquids, which results in highly stable magnetic fluids. The new fluids are compared with classical organic fluids stabilized by oleic acid (OA). Magnetic granulometry and small-angle neutron scattering (polarized mode) reveal a great difference in the particle size distribution function for the studied magnetic fluids, particularly a decrease in the characteristic particle radius of magnetite when lauric and myristic acids are used instead of OA.

  8. The altered glucose metabolism in tumor and a tumor acidic microenvironment associated with extracellular matrix metalloproteinase inducer and monocarboxylate transporters

    PubMed Central

    Li, Xiaofeng; Yu, Xiaozhou; Dai, Dong; Song, Xiuyu; Xu, Wengui

    2016-01-01

    Extracellular matrix metalloproteinase inducer, also knowns as cluster of differentiation 147 (CD147) or basigin, is a widely distributed cell surface glycoprotein that is involved in numerous physiological and pathological functions, especially in tumor invasion and metastasis. Monocarboxylate transporters (MCTs) catalyze the proton-linked transport of monocarboxylates such as L-lactate across the plasma membrane to preserve the intracellular pH and maintain cell homeostasis. As a chaperone to some MCT isoforms, CD147 overexpression significantly contributes to the metabolic transformation of tumor. This overexpression is characterized by accelerated aerobic glycolysis and lactate efflux, and it eventually provides the tumor cells with a metabolic advantage and an invasive phenotype in the acidic tumor microenvironment. This review highlights the roles of CD147 and MCTs in tumor cell metabolism and the associated molecular mechanisms. The regulation of CD147 and MCTs may prove to be with a therapeutic potential for tumors through the metabolic modification of the tumor microenvironment. PMID:27009812

  9. Unusual effects of monocarboxylic acids on the structure and on the transport and mechanical properties of chitosan films.

    PubMed

    Chen, Fei; Gällstedt, Mikael; Olsson, Richard T; Gedde, Ulf W; Hedenqvist, Mikael S

    2015-11-01

    The purpose of this study was to study the transport of monocarboxylic acids in chitosan films, since this is important for understanding and predicting the drying kinetics of chitosan from aqueous solutions. Despite the wealth of data on chitosan films prepared from aqueous monocarboxylic acid solutions, this transport has not been reported. Chitosan films were exposed to formic, acetic, propionic and butyric acid vapours, it was found that the rate of uptake decreased with increasing molecular size. The equilibration time was unexpectedly long, especially for propionic and butyric acid, nine months. A clear two-stage uptake curve was observed for propionic acid. Evidently, the rate of uptake was determined by acid-induced changes in the material. X-ray diffraction and infrared spectroscopy indicated that the structure of the chitosan acetate and buffered chitosan films changed during exposure to acid and during the subsequent drying. The dried films previously exposed to the acid showed less crystalline features than the original material and a novel repeating structure possibly involving acid molecules. The molar mass of the chitosan decreased on exposure to acid but tensile tests revealed that the films were always ductile. The films exposed to acid vapour (propionic and butyric acid) for the longest period of time were insoluble in the size-exclusion chromatography eluent, and they were also the most ductile/extensible of all samples studied.

  10. Lactic acid production in Saccharomyces cerevisiae is modulated by expression of the monocarboxylate transporters Jen1 and Ady2.

    PubMed

    Pacheco, António; Talaia, Gabriel; Sá-Pessoa, Joana; Bessa, Daniela; Gonçalves, Maria José; Moreira, Roxana; Paiva, Sandra; Casal, Margarida; Queirós, Odília

    2012-05-01

    We aimed to manipulate the metabolism of Saccharomyces cerevisiae to produce lactic acid and search for the potential influence of acid transport across the plasma membrane in this process. Saccharomyces cerevisiae W303-1A is able to use l-lactic acid but its production in our laboratory has not previously been detected. When the l-LDH gene from Lactobacillus casei was expressed in S. cerevisiae W303-1A and in the isogenic mutants jen1∆, ady2∆ and jen1∆ ady2∆, all strains were able to produce lactic acid, but higher titres were achieved in the mutant strains. In strains constitutively expressing both LDH and JEN1 or ADY2, a higher external lactic acid concentration was found when glucose was present in the medium, but when glucose was exhausted, its consumption was more pronounced. These results demonstrate that expression of monocarboxylate permeases influences lactic acid production. Ady2 has been previously characterized as an acetate permease but our results demonstrated its additional role in lactate uptake. Overall, we demonstrate that monocarboxylate transporters Jen1 and Ady2 are modulators of lactic acid production and may well be used to manipulate lactic acid export in yeast cells.

  11. Unsaturated C3,5,7,9-Monocarboxylic Acids by Aqueous, One-Pot Carbon Fixation: Possible Relevance for the Origin of Life.

    PubMed

    Scheidler, Christopher; Sobotta, Jessica; Eisenreich, Wolfgang; Wächtershäuser, Günter; Huber, Claudia

    2016-06-10

    All scientific approaches to the origin of life share a common problem: a chemical path to lipids as main constituents of extant cellular enclosures. Here we show by isotope-controlled experiments that unsaturated C3,5,7,9-monocarboxylic acids form by one-pot reaction of acetylene (C2H2) and carbon monoxide (CO) in contact with nickel sulfide (NiS) in hot aqueous medium. The primary products are toto-olefinic monocarboxylic acids with CO-derived COOH groups undergoing subsequent stepwise hydrogenation with CO as reductant. In the resulting unsaturated monocarboxylic acids the double bonds are mainly centrally located with mainly trans-configuration. The reaction conditions are compatible with an origin of life in volcanic-hydrothermal sub-seafloor flow ducts.

  12. Unsaturated C3,5,7,9-Monocarboxylic Acids by Aqueous, One-Pot Carbon Fixation: Possible Relevance for the Origin of Life

    PubMed Central

    Scheidler, Christopher; Sobotta, Jessica; Eisenreich, Wolfgang; Wächtershäuser, Günter; Huber, Claudia

    2016-01-01

    All scientific approaches to the origin of life share a common problem: a chemical path to lipids as main constituents of extant cellular enclosures. Here we show by isotope-controlled experiments that unsaturated C3,5,7,9-monocarboxylic acids form by one-pot reaction of acetylene (C2H2) and carbon monoxide (CO) in contact with nickel sulfide (NiS) in hot aqueous medium. The primary products are toto-olefinic monocarboxylic acids with CO-derived COOH groups undergoing subsequent stepwise hydrogenation with CO as reductant. In the resulting unsaturated monocarboxylic acids the double bonds are mainly centrally located with mainly trans-configuration. The reaction conditions are compatible with an origin of life in volcanic-hydrothermal sub-seafloor flow ducts. PMID:27283227

  13. Freeze-out extraction of monocarboxylic acids from water into acetonitrile under the action of centrifugal forces

    NASA Astrophysics Data System (ADS)

    Bekhterev, V. N.

    2016-10-01

    It is established that the efficiency of the freezing-out extraction of monocarboxylic acids C3-C;8 and sorbic acid from water into acetonitrile increases under the action of centrifugal forces. The linear growth of the partition coefficient in the homologous series of C2-C8 acids with an increase in molecule length, and the difference between the efficiency of extracting sorbic and hexanoic acid, are discussed using a theoretical model proposed earlier and based on the adsorption-desorption equilibrium of the partition of dissolved organic compounds between the resulting surface of ice and the liquid phase of the extract. The advantages of the proposed technique with respect to the degree of concentration over the method of low-temperature liquid-liquid extraction are explained in light of the phase diagram for the water-acetonitrile mixture.

  14. Decarboxylative Fluorination of Aliphatic Carboxylic Acids via Photoredox Catalysis

    PubMed Central

    Ventre, Sandrine; Petronijevic, Filip R.; MacMillan, David W. C.

    2016-01-01

    The direct conversion of aliphatic carboxylic acids to the corresponding alkyl fluorides has been achieved via visible light-promoted photoredox catalysis. This operationally simple, redox-neutral fluorination method is amenable to a wide variety of carboxylic acids. Photon-induced oxidation of carboxylates leads to the formation of carboxyl radicals, which upon rapid CO2-extrusion and F• transfer from a fluorinating reagent yield the desired fluoroalkanes with high efficiency. Experimental evidence indicates that an oxidative quenching pathway is operable in this broadly applicable fluorination protocol. PMID:25881929

  15. Extraction of manganese by alkyl monocarboxylic acid in a mixed extractant from a leaching solution of spent lithium-ion battery ternary cathodic material

    NASA Astrophysics Data System (ADS)

    Joo, Sung-Ho; Shin, Dongju; Oh, ChangHyun; Wang, Jei-Pil; Shin, Shun Myung

    2016-02-01

    We investigate the separation of manganese by an antagonistic effect from a leaching solution of ternary cathodic material of spent lithium-ion batteries that contain 11,400 mg L-1 Co, 11,700 mg L-1 Mn, 12,200 mg L-1 Ni, and 5300 mg L-1 Li using a mixture of alkyl monocarboxylic acid and di-(2-ethylhexyl)phosphoric acid extractants. pH isotherm, distribution coefficient, separation factor, McCabe-Thiele diagram, selective scrubbing, and countercurrent extraction tests are carried out to prove an antagonistic effect and to recover manganese using alkyl monocarboxylic in the mixed extractant. Slope analysis is used to determine the extraction mechanism between a mixture of extractants and valuable metals. An increasing concentration of alkyl monocarboxylic acid in the mixture of extractants results in a decrease in distribution coefficient of cobalt and manganese, however, the separation factor value (β(Mn/Co)) increases at pH 4.5. This is caused by slope analysis where alkyl monocarboxylic acid disrupts the extraction mechanism between di-(2-ethylhexyl)phosphoric acid and cobalt. Finally, continuous countercurrent extraction in a mini-plant test demonstrate the feasibility of manganese recovery from cobalt, nickel, and lithium.

  16. Polarized Raman spectra and intensities of aliphatic amino acids

    NASA Astrophysics Data System (ADS)

    Himmler, Hans J.; Eysel, Hans H.

    1989-01-01

    Raman spectra of aliphatic α- L-amino acids, glycine, alanine, and valine were re-investigated both in aqueous solution and deuterium oxide solution. The spectra were taken of the zwitterionic and of the completely deprotonated form of the amino acids. Spectra of leucine and isoleucine were studied in water at the isoelectric point. Spectra were recorded both with parallel and perpendicular polarization and the isotropic and anisotropic scattering components were isolated. The integrated intensities of CH stretch, CC stretch and carboxylate bend vibrations are discussed. Linear relations between the number of CC and CH bonds and the total scattered intensity in the appropriate spectral regions are observed. The sum over the carboxylate modes shows characteristic intensities for the first three members of the aliphatic amino acids. An increase of isotropic scattering of ϱ co 2 near 510 cm -1 with increasing chain length of the amino acid (or with increasing concentration) is interpreted as the result of micelle formation.

  17. Aqueous infrared carboxylate absorbances: Aliphatic di-acids

    USGS Publications Warehouse

    Cabaniss, S.E.; Leenheer, J.A.; McVey, I.F.

    1998-01-01

    Aqueous attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of 18 aliphatic di-carboxylic acids are reported as a function of pH. The spectra show isosbestic points and intensity changes which indicate that Beer's law is obeyed, and peak frequencies lie within previously reported ranges for aqueous carboxylates and pure carboxylic acids. Intensity sharing from the symmetric carboxylate stretch is evident in many cases, so that bands which are nominally due to alkyl groups show increased intensity at higher pH. The asymmetric stretch of the HA- species is linearly related to the microscopic acidity constant of the H2A species, with ??pK 2 intervening atoms). The results suggest that aqueous ATR-FTIR may be able to estimate 'intrinsic' pKa values of carboxylic acids, in addition to providing quantitative estimates of ionization. ?? 1998 Elsevier Science B.V. All rights reserved.

  18. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... salt (generic). 721.2098 Section 721.2098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under...

  19. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... salt (generic). 721.2098 Section 721.2098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under...

  20. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... salt (generic). 721.2098 Section 721.2098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under...

  1. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... salt (generic). 721.2098 Section 721.2098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under...

  2. 40 CFR 721.2098 - Aliphatic polycarboxylic acid metal salt (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... salt (generic). 721.2098 Section 721.2098 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2098 Aliphatic polycarboxylic acid metal salt (generic). (a) Chemical... as an aliphatic polycarboxylic acid metal salt (PMN P-01-7) is subject to reporting under...

  3. Regulation of monocarboxylic acid transporter-1 by cAMP dependent vesicular trafficking in brain microvascular endothelial cells.

    PubMed

    Uhernik, Amy L; Li, Lun; LaVoy, Nathan; Velasquez, Micah J; Smith, Jeffrey P

    2014-01-01

    In this study, a detailed characterization of Monocarboxylic Acid Transporter-1 (Mct1) in cytoplasmic vesicles of cultured rat brain microvascular endothelial cells shows them to be a diverse population of endosomes intrinsic to the regulation of the transporter by a brief 25 to 30 minute exposure to the membrane permeant cAMP analog, 8Br-cAMP. The vesicles are heterogeneous in size, mobility, internal pH, and co-localize with discreet markers of particular types of endosomes including early endosomes, clathrin coated vesicles, caveolar vesicles, trans-golgi, and lysosomes. The vesicular localization of Mct1 was not dependent on its N or C termini, however, the size and pH of Mct1 vesicles was increased by deletion of either terminus demonstrating a role for the termini in vesicular trafficking of Mct1. Using a novel BCECF-AM based assay developed in this study, 8Br-cAMP was shown to decrease the pH of Mct1 vesicles after 25 minutes. This result and method were confirmed in experiments with a ratiometric pH-sensitive EGFP-mCherry dual tagged Mct1 construct. Overall, the results indicate that cAMP signaling reduces the functionality of Mct1 in cerebrovascular endothelial cells by facilitating its entry into a highly dynamic vesicular trafficking pathway that appears to lead to the transporter's trafficking to autophagosomes and lysosomes.

  4. Regulation of Monocarboxylic Acid Transporter-1 by cAMP Dependent Vesicular Trafficking in Brain Microvascular Endothelial Cells

    PubMed Central

    Uhernik, Amy L.; Li, Lun; LaVoy, Nathan; Velasquez, Micah J.; Smith, Jeffrey P.

    2014-01-01

    In this study, a detailed characterization of Monocarboxylic Acid Transporter-1 (Mct1) in cytoplasmic vesicles of cultured rat brain microvascular endothelial cells shows them to be a diverse population of endosomes intrinsic to the regulation of the transporter by a brief 25 to 30 minute exposure to the membrane permeant cAMP analog, 8Br-cAMP. The vesicles are heterogeneous in size, mobility, internal pH, and co-localize with discreet markers of particular types of endosomes including early endosomes, clathrin coated vesicles, caveolar vesicles, trans-golgi, and lysosomes. The vesicular localization of Mct1 was not dependent on its N or C termini, however, the size and pH of Mct1 vesicles was increased by deletion of either terminus demonstrating a role for the termini in vesicular trafficking of Mct1. Using a novel BCECF-AM based assay developed in this study, 8Br-cAMP was shown to decrease the pH of Mct1 vesicles after 25 minutes. This result and method were confirmed in experiments with a ratiometric pH-sensitive EGFP-mCherry dual tagged Mct1 construct. Overall, the results indicate that cAMP signaling reduces the functionality of Mct1 in cerebrovascular endothelial cells by facilitating its entry into a highly dynamic vesicular trafficking pathway that appears to lead to the transporter's trafficking to autophagosomes and lysosomes. PMID:24454947

  5. Steric hindrance of 2,6-disubstituted benzoic acid derivatives on the uptake via monocarboxylic acid transporters from the apical membranes of Caco-2 cells.

    PubMed

    Tsukagoshi, Kensuke; Kimura, Osamu; Endo, Tetsuya

    2014-05-01

    Benzoic acid is a typical substrate for monocarboxylic acid transporters (MCTs), and easily taken up from the apical membranes of Caco-2 cells by MCTs. However, some benzoic acid derivatives were sparingly taken up by Caco-2 cells. To elucidate the mechanism of lower uptake of the derivatives, we investigated the effect of substitution of benzene ring on the uptake by MCTs using Caco-2 cells. Among the benzoic acid derivatives tested, the uptake of 2,6-disubstituted benzoic acids was markedly lower than that of other benzoic acids. Co-incubation of the 2,6-disubstituted derivatives with benzoic acid did not decrease the uptake of benzoic acid, while co-incubation with other derivatives significantly decreased the uptake of benzoic acid. Kinetic analyses elucidated that the uptake of 2,6-dichlorobenzoic acid and 2,3,6-trichlorobenzoic acid did not involve the carrier-mediated process. The 2,6-disubstitution of benzoic acid may prevent the access of carboxylic acid group to MCTs expressed on the apical membranes of Caco-2 cells. PMID:24861932

  6. Enhanced crystallization of poly (lactic acid) through reactive aliphatic bisamide

    NASA Astrophysics Data System (ADS)

    Nanthananon, P.; Seadan, M.; Pivsa-Art, S.; Suttiruengwong, S.

    2015-07-01

    The poor crystallization rate of poly (lactic acid) (PLA) is a major drawback in terms of controlling the properties of final products. To overcome this, a nucleating agent is normally applied. In this work, the aliphatic bisamide, N, N'-(1,3-propylene) bis(10-undecenamide) (PBU), having reactive functional groups is used as a crystallization promoter for PLA by adding PBU in various concentration (0.1-0.7 wt%) into PLA together with peroxide via reactive melt blending. The conventional ethylene bis-stearamide(EBS) is used for a comparison. The extruded samples are characterized for gel content and FT-IR spectroscopy. The crystallization behaviour and rate, and spherulites morphology are investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. It is found that the addition of PBU into PLA results in the dramatic increase in crystallinity and crystallization rate of PLA compared with neat PLA and PLA added EBS. The crystallinity increases to 24.9-28.3% higher than neat PLA under even cooling rate of 7°C/min. The addition of 0.7 wt% PBU shows the fastest crystallization rate with t1/2 value isothermally crystallized at 130°C of only 6 min. POM images indicate the increase in the nucleation density and very fine spherulitesof PLA added PBU, promoting the fast crystallization.

  7. Butyric acid increases transepithelial transport of ferulic acid through upregulation of the monocarboxylate transporters SLC16A1 (MCT1) and SLC16A3 (MCT4).

    PubMed

    Ziegler, Kerstin; Kerimi, Asimina; Poquet, Laure; Williamson, Gary

    2016-06-01

    Ferulic acid is released by microbial hydrolysis in the colon, where butyric acid, a major by-product of fermentation, constitutes the main energy source for colonic enterocytes. We investigated how varying concentrations of this short chain fatty acid may influence the absorption of the phenolic acid. Chronic treatment of Caco-2 cells with butyric acid resulted in increased mRNA and protein abundance of the monocarboxylate transporters SLC16A1 (MCT1) and SLC16A3 (MCT4), previously proposed to facilitate ferulic acid absorption in addition to passive diffusion. Short term incubation with butyric acid only led to upregulation of MCT4 while both conditions increased transepithelial transport of ferulic acid in the apical to basolateral, but not basolateral to apical, direction. Chronic treatment also elevated intracellular concentrations of ferulic acid, which in turn gave rise to increased concentrations of ferulic acid metabolites. Immunofluorescence staining of cells revealed uniform distribution of MCT1 protein in the cell membrane, whereas MCT4 was only detected in the lateral plasma membrane sections of Caco-2 cells. We therefore propose that MCT1 may be acting as an uptake transporter and MCT4 as an efflux system across the basolateral membrane for ferulic acid, and that this process is stimulated by butyric acid. PMID:26854723

  8. Upper limit of urea adduct formation with methyl esters of n-monocarboxylic acids

    SciTech Connect

    Matsihev, V.A.

    1984-03-01

    This article attempts to determine the temperature of the upper limit of urea formation (ULA) with methyl esters as a function of the number of carbon atoms in their molecules; the ULA temperature of these same esters in binary mixtures with esters of lower molecular weight as a function of the weight concentration of the latter; and the ULA temperature of esters in multicomponent mixtures with esters of lower molecular weight as a function of their partial weight concentrations. Binary mixtures of the esters were investigated with concentrations of the second component (ester with lower molecular weight) of 0-99% by weight, using the same reactants as those used in investigating the original compounds. The dependence of the ULA temperature of the primary component of the binary mixture on the weight concentration of the secondary component is described by a nonlinear equation. The results show that compounds of any homologous series having a normal aliphatic chain, with an interval of carbon numbers that is strictly determined for each such series, from adducts with crystalline urea in accordance with identical laws for individual compounds, binary mixtures, and multicomponent mixtures. Includes 2 tables.

  9. Biodegradation and metabolic pathway of β-chlorinated aliphatic acid in Bacillus sp. CGMCC no. 4196.

    PubMed

    Lin, Chunjiao; Yang, Lirong; Xu, Gang; Wu, Jianping

    2011-04-01

    In this study, a bacterial Bacillus sp. CGMCC no. 4196 was isolated from mud. This strain exhibited the ability to degrade high concentration of 3-chloropropionate (3-CPA, 120 mM) or 3-chlorobutyrate (30 mM), but not chloroacetate or 2-chloropropionate (2-CPA). The growing cells, resting cells, and cell-free extracts from this bacterium had the capability of 3-CPA degradation. The results indicated that the optimum biocatalyst for 3-CPA biodegradation was the resting cells. The 3-CPA biodegradation pathway was further studied through the metabolites and critical enzymes analysis by HPLC, LC-MS, and colorimetric method. The results demonstrated that the metabolites of 3-CPA were 3-hydroxypropionic acid (3-HP) and malonic acid semialdehyde, and the critical enzymes were 3-CPA dehalogenase and 3-HP dehydroxygenase. Thus, the mechanism of the dehalogenase-catalyzed reaction was inferred as hydrolytic dehalogenation which was coenzyme A-independent and oxygen-independent. Finally, the pathway of β-chlorinated aliphatic acid biodegradation could be concluded as follows: the β-chlorinated acid is first hydrolytically dehalogenated to the β-hydroxyl aliphatic acid, and the hydroxyl aliphatic acid is oxidized to β-carbonyl aliphatic acid by β-hydroxy aliphatic acid dehydroxygenase. It is the first report that 3-HP was produced from 3-CPA by β-chlorinated aliphatic acid dehalogenase.

  10. Stable vesicles composed of monocarboxylic or dicarboxylic fatty acids and trimethylammonium amphiphiles.

    PubMed

    Caschera, F; Bernardino de la Serna, J; Löffler, P M G; Rasmussen, T E; Hanczyc, M M; Bagatolli, L A; Monnard, P-A

    2011-12-01

    The self-assembly of cationic and anionic amphiphile mixtures into vesicles in aqueous media was studied using two different systems: (i) decanoic acid and trimethyldecylammonium bromide and (ii) hexadecanedioic acid (a simple bola-amphiphile) and trimethyldecylammonium bromide. The resulting vesicles with varying amphiphile ratios were characterized using parameters such as the critical vesicle concentration, pH sensitivity, and encapsulation efficiency. We also produced and observed giant vesicles from these mixtures using the electroformation method and confocal microscopy. The mixed catanionic vesicles were shown to be more stable than those formed by pure fatty acids. Those containing bola-amphiphile even showed the encapsulation of a small hydrophilic solute (8-hydroxypyrene-1,3,6-trisulfonic-acid), suggesting a denser packing of the amphiphiles. Compression and kinetics analysis of monolayers composed of these amphiphiles mixtures at the air/water interface suggests that the stabilization of the structures can be attributed to two main interactions between headgroups, predominantly the formation of hydrogen bonds between protonated and deprotonated acids and the additional electrostatic interactions between ammonium and acid headgroups. PMID:21932777

  11. The role of essential fatty acids in development

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fatty acids are aliphatic monocarboxylic acids. They are classified as saturated, monounsaturated, or polyunsaturated fatty acids depending upon the number of double bonds in the carbon chain. Saturated fatty acids have no double bonds, monounsaturated fatty acids have 1 double bond, and polyunsat...

  12. Structure of seven organic salts assembled from 2,6-diaminopyridine with monocarboxylic acids, dicarboxylic acids, and tetracarboxylic acids

    NASA Astrophysics Data System (ADS)

    Gao, Xingjun; Zhang, Huan; Wen, Xianhong; Liu, Bin; Jin, Shouwen; Wang, Daqi

    2015-08-01

    Studies concentrating on non-covalent interactions between the organic base of 2,6-diaminopyridine, and carboxylic acids have led to an increased understanding of the role 2,6-diaminopyridine in binding with carboxylic acid derivatives. Here anhydrous and hydrated multi-component organic acid-base salts of 2,6-diaminopyridine have been prepared with the carboxylic acids as nicotinic acid, o-chlorobenzoic acid, 1,3-benzodioxole-5-carboxylic acid, 3,5-dinitrosalicylic acid, 4-nitro-phthalic acid, 1,4-cyclohexanedicarboxylic acid, and butane-1,2,3,4-tetracarboxylic acid. The seven crystalline compounds were characterized by X-ray diffraction analysis, infrared (IR), melting point (mp), and elemental analysis. All structures adopted the hetero R22(8) supramolecular synthons. The supramolecular architectures bear extensive Nsbnd H⋯N, Osbnd H⋯N, Osbnd H⋯O, Nsbnd H⋯O, and CH⋯O associations as well as other nonbonding contacts as CHsbnd N, CH2sbnd O, π-π, C-π, O-π, Cl-π, Clsbnd O, and Osbnd O interactions. The role of weak and strong hydrogen bonding in the crystal packing is ascertained.

  13. Monocarboxylic acids from oxidation of acyclic isoprenoid alkanes by Mycobacterium fortuitum

    NASA Technical Reports Server (NTRS)

    Cox, R. E.; Maxwell, J. R.; Myers, R. N.

    1976-01-01

    Mycobacterium fortuitum utilizes certain stereoisomeric mixtures of individual multimethyl branched alkanes as sole carbon source, including 2,6(R), 10(S), 14(RS)-tetramethylhexadecane; 2,6(R), 10(S), 14(RS)-tetramethylheptadecane; 2,6(RS), 10(RS)-trimethyltetradecane, and 2,6(R), 10(S)-trimethylpentadecane. Products of oxidation isolated from the bacterial lipids were acids derived predominantly from oxidation of the isopropyl terminus of each alkane, except in the case of 2,6(RS), 10(RS)-trimethyltetradecane. With the latter, acids from oxidation at either terminus were detected in comparable proportions.

  14. New insight on aliphatic linkages in the macromolecular organic fraction of Orgueil and Murchison meteorites through ruthenium tetroxide oxidation

    NASA Astrophysics Data System (ADS)

    Remusat, Laurent; Derenne, Sylvie; Robert, François

    2005-09-01

    Ruthenium tetroxide oxidation was used to examine the macromolecular insoluble organic matter (IOM) from the Orgueil and Murchison meteorites and especially to characterize the aliphatic linkages. Already applied to various terrestrial samples, ruthenium tetroxide is a selective oxidant which destroys aromatic units, converting them into CO 2, and yields aliphatic and aromatic acids. In our experiment on chondritic IOM, it produces mainly short aliphatic diacids and polycarboxylic aromatic acids. Some short hydroxyacids are also detected. Aliphatic diacids are interpreted as aliphatic bridges between aromatic units in the chemical structure, and polycarboxylic aromatic acids are the result of the fusion of polyaromatic units. The product distribution shows that aliphatic links are short with numerous substitutions. No indigenous monocarboxylic acid was detected, showing that free aliphatic chains must be very short (less than three carbon atoms). The hydroxyacids are related to the occurrence of ester and ether functional groups within the aliphatic bridges between the aromatic units. This technique thus allows us to characterize in detail the aliphatic linkages of the IOMs, and the derived conclusions are in agreement with spectroscopic, pyrolytic, and degradative results previously reported. Compared to terrestrial samples, the aliphatic part of chondritic IOM is shorter and highly substituted. Aromatic units are smaller and more cross-linked than in coals, as already proposed from NMR data. Orgueil and Murchison IOM exhibit some tiny differences, especially in the length of aliphatic chains.

  15. On the microstructure of organic solutions of mono-carboxylic acids: Combined study by infrared spectroscopy, small-angle neutron scattering and molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Eremin, Roman A.; Kholmurodov, Kholmirzo T.; Petrenko, Viktor I.; Rosta, László; Grigoryeva, Natalia A.; Avdeev, Mikhail V.

    2015-11-01

    The data of infrared spectroscopy (IR), molecular dynamics (MD) simulations and small-angle neutron scattering (SANS) have been combined to conclude about the nanoscale structural organization of organic non-polar solutions of saturated mono-carboxylic acids with different alkyl chain lengths for diluted solutions of saturated myristic (C14) and stearic (C18) acids in benzene and decalin. In particular, the degree of dimerization was found from the IR spectra. The structural anisotropy of the acids and their dimers was used in the treatment of the data of MD simulations to describe the solute-solvent interface in a cylindrical approximation and show its rather strong influence on SANS. The corresponding scattering length density profiles were used to fit the experimental SANS data comprising the information about the acid molecule isomerization. The SANS data from concentrated solutions showed a partial self-assembling of the acids within the nematic transition is different for two solvents due to lyophobic peculiarities.

  16. Uptake of 4-chloro-2-methylphenoxyacetic acid (MCPA) from the apical membrane of Caco-2 cells by the monocarboxylic acid transporter

    SciTech Connect

    Kimura, Osamu; Tsukagoshi, Kensuke; Endo, Tetsuya

    2008-03-15

    The cellular uptake mechanism of 4-chloro-2-methylphenoxyacetic acid (MCPA), a phenoxyacetic acid derivative, was investigated using Caco-2 epithelial cells. The cells were incubated with 50 {mu}M MCPA at pH 6.0 and 37 deg. C, and the uptake of MCPA from the apical membranes was measured. The uptake of MCPA was significantly decreased by incubation at low temperature (4 {sup o}C) and markedly increased by lowering the extracellular pH. Pretreatment with a protonophore, carbonylcyanide-p-(trifluoromethoxy)phenylhydrazone (25 {mu}M), or metabolic inhibitors, 2,4-dinitrophenol (1 mM) and sodium azide (10 mM), significantly decreased the uptake of MCPA by 53%, 45% and 48%, respectively. Coincubation of MCPA with 10 mM L-lactic acid or {alpha}-cyano-4-hydroxycinnamate, which is a substrate or an inhibitor of the monocarboxylic acid transporters (MCTs), significantly decreased the uptake of MCPA by 31% and 20%, respectively, and coincubation with benzoic acid profoundly decreased the uptake by 68%. In contrast, coincubation with succinic acid (a dicarboxylic acid) did not affect the uptake. Kinetic analysis of initial MCPA uptake suggested that MCPA is taken up via a carrier-mediated process [K{sub m} = 1.37 {+-} 0.15 mM, V{sub max} = 115 {+-} 6 nmol (mg protein){sup -1} (3 min){sup -1}]. Lineweaver-Burk plots show that benzoic acid competitively inhibits the uptake of MCPA with a K{sub i} value of 4.68 {+-} 1.76 mM. A trans-stimulation effect on MCPA uptake was found in cells preloaded with benzoic acid. These results suggest that the uptake of MCPA from the apical membrane of Caco-2 cells is mainly mediated by common MCTs along with benzoic acid but also in part by L-lactic acid.

  17. Phenolic and short-chained aliphatic organic acid constituents of wild oat (Avena fatua L.) seeds.

    PubMed

    Gallagher, R S; Ananth, R; Granger, K; Bradley, B; Anderson, J V; Fuerst, E P

    2010-01-13

    The objective of this research was to identify and quantify the phenolic and short-chained aliphatic organic acids present in the seeds of three wild-type populations of wild oat and compare these results to the chemical composition of seeds from two commonly utilized wild oat isolines (M73 and SH430). Phenolic acids have been shown to serve as germination inhibitors, as well as protection for seeds from biotic and abiotic stress factors in other species, whereas aliphatic organic acids have been linked to germination traits and protection against pathogens. Wild oat populations were grown under a "common garden" environment to remove maternal variation, and the resulting seeds were extracted to remove the readily soluble and chemically bound phenolic and aliphatic organic acid components. Compounds were identified and quantified using gas chromatography-mass spectrometry. Ferulic and p-coumaric acid comprised 99% of the total phenolic acids present in the seeds, of which 91% were contained in the hulls and 98% were in the chemically bound forms. Smaller quantities of OH benzoic and vanillic acid were also detected. Soluble organic acids concentrations were higher in the M73 isoline compared to SH430, suggesting that these chemical constituents could be related to seed dormancy. Malic, succinic, fumaric and azelaic acid were the dominant aliphatic organic acids detected in all seed and chemical fractions.

  18. A mitochondrial monocarboxylate transporter in rat liver and heart and its possible function in cell control.

    PubMed Central

    Mowbray, J

    1975-01-01

    Several hydroxy- and keto-substituted monocarboxylates were found to undergo co- as well as counter-exchange across the mitochondrial membrane. The results argue against a simple Donnan system and may be explained by the existence of a transporter for monocarboxylates. In support of this explanation it was apparently possible to 'pump' pyruvate to the sucrose-inaccessible space by using the dicarboxylate transporter. Further, several aromatic and aliphatic analogues of pyruvate, but not of di- or tri-carboxylate transport inhibitors, have been shown to prevent pyruvate-exchange reactions. Palmitoylcarnitine was found to have a much stronger affinity for the carrier than either carnitine or pyruvate and the possible consequences of this for carnitine-palmitoylcarnitine exchange and on the control of the pyruvate dehydrogenase complex are explored. In view of the range of transport inhibitors and substrates it is suggested that the carrier has a fairly broad specificity. 'Inhibitor-stop' kinetic studies show that the speed of translocation of pyruvate at 1 degrees C is of the same order as malate. The possible correlation between the role of a hydroxy-keto acid transporter in substrate exchange and some whole animal experiments is briefly discussed. It is proposed that for reasons of control the cell will require membrane monocarboxylate transporters no less than di- or tri-carboxylate carriers. PMID:1156399

  19. Mass spectral analysis of C3 and C4 aliphatic amino acid derivatives.

    NASA Technical Reports Server (NTRS)

    Lawless, J. G.; Chadha, M. S.

    1971-01-01

    Diagnostic criteria are obtained for the distinction of alpha, beta, gamma, and N-methyl isomers of the C3 and C4 aliphatic amino acids, using mass spectral analysis of the derivatives of these acids. The use of deuterium labeling has helped in the understanding of certain fragmentation pathways.

  20. 40 CFR 721.10188 - Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Fatty acids, tall-oil, reaction... Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine (generic). (a... generically as fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

  1. 40 CFR 721.10188 - Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Fatty acids, tall-oil, reaction... Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine (generic). (a... generically as fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

  2. 40 CFR 721.10188 - Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fatty acids, tall-oil, reaction... Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine (generic). (a... generically as fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

  3. 40 CFR 721.10188 - Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Fatty acids, tall-oil, reaction... Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine (generic). (a... generically as fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

  4. 40 CFR 721.10188 - Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Fatty acids, tall-oil, reaction... Fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine (generic). (a... generically as fatty acids, tall-oil, reaction products with 4-methyl-2-pentanone and aliphatic polyamine...

  5. Distribution and occurrence of aliphatic acid anions in deep subsurface waters

    SciTech Connect

    Fisher, J.B.

    1987-09-01

    This study reports 144 new analyses of short-chain aliphatic acid anions (acetate, propionate, butyrate, and valerate) in formation waters from eight localities: Eastern Venezuelan Basin, Denver Basin, Eastern Green River Basin, San Juan Basin, Piceance Basin, Raton Basin, Gulf Coast Basin, and the Western Overthrust. Reservoir temperature does not predict total or relative abundance of aliphatic acid anions, but does predict maximum total concentrations of these species. Maximum concentrations increase to approx. 90/sup 0/C. Above approx. 90/sup 0/C, maximum concentrations decrease. Above approx. 250/sup 0/C, maximum concentrations should not exceed approx. 1 mg/l. The general order of dominance is acetate >> propionate > butyrate > valerate, but for coal-associated waters is propionate greater than or equal to acetate > butyrate > valerate. Lack of longer-chain aliphatic acid anion dominance over acetate at low reservoir temperatures may suggest hydrologic communication with deeper reservoirs.

  6. Silver-Catalyzed Decarboxylative Radical Azidation of Aliphatic Carboxylic Acids in Aqueous Solution.

    PubMed

    Liu, Chao; Wang, Xiaoqing; Li, Zhaodong; Cui, Lei; Li, Chaozhong

    2015-08-12

    We report herein an efficient and general method for the decarboxylative azidation of aliphatic carboxylic acids. Thus, with AgNO3 as the catalyst and K2S2O8 as the oxidant, the reactions of various aliphatic carboxylic acids with tosyl azide or pyridine-3-sulfonyl azide in aqueous CH3CN solution afforded the corresponding alkyl azides under mild conditions. A broad substrate scope and wide functional group compatibility were observed. A radical mechanism is proposed for this site-specific azidation.

  7. New aliphatic alcohol and (Z)-4-coumaric acid glycosides from Acanthus ilicifolius.

    PubMed

    Wu, Jun; Zhang, Si; Huang, Jianshe; Xiao, Qiang; Li, Qingxin; Long, Lijuan; Huang, Liangmin

    2003-10-01

    From the aerial parts of Acanthus ilicifolius, a new aliphatic alcohol glycoside (ilicifolioside C) and two new (Z)-4-coumaric acid glycosides, (Z)-4-coumaric acid 4-O-beta-D-glucopyranoside and (Z)-4-coumaric acid 4-O-beta-D-apiofuranosyl-(1"-->2')-O-beta-D-glucopyranoside were isolated. The structural elucidations were based on the analyses of spectroscopic data. Z-Form 4-coumaric acid glycosides were first isolated from plant.

  8. 40 CFR 721.10289 - Hexanedioic acid polymer with aliphatic polyol dihydrogen phosphate aromatic ester (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hexanedioic acid polymer with aliphatic polyol dihydrogen phosphate aromatic ester (generic). 721.10289 Section 721.10289 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New...

  9. 40 CFR 721.10289 - Hexanedioic acid polymer with aliphatic polyol dihydrogen phosphate aromatic ester (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hexanedioic acid polymer with aliphatic polyol dihydrogen phosphate aromatic ester (generic). 721.10289 Section 721.10289 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New...

  10. 40 CFR 721.10289 - Hexanedioic acid polymer with aliphatic polyol dihydrogen phosphate aromatic ester (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hexanedioic acid polymer with aliphatic polyol dihydrogen phosphate aromatic ester (generic). 721.10289 Section 721.10289 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New...

  11. Application of headspace solid-phase microextraction followed by gas chromatography-mass spectrometry to determine short-chain alkane monocarboxylic acids in aqueous samples.

    PubMed

    Banel, Anna; Wasielewska, Marta; Zygmunt, Bogdan

    2011-03-01

    In this study, a procedure was developed to determine short-chain alkane monocarboxylic acids (SCMAs) in aqueous samples using headspace solid-phase microextraction (HS-SPME) followed by gas chromatography (GC) coupled with mass spectrometry (MS). A Stabilwax-DA capillary column (30 m × 0.32-mm inner diameter, 0.50-μm film thickness) was used for GC separation and a 60-μm poly(ethylene glycol) fiber was used to isolate SCMAs from water and introduce them into the gas chromatograph. Parameters of HS-SPME, analyte desorption, and GC-MS analysis were selected and an analytical procedure was proposed. Limits of quantitation were on the order of about 0.2 mg L(-1). As an example of the application of the procedure, SCAMs were determined in municipal wastewater at different steps of treatment.

  12. Transport of monocarboxylic acids at the blood-brain barrier: Studies with monolayers of primary cultured bovine brain capillary endothelial cells

    SciTech Connect

    Terasaki, T.; Takakuwa, S.; Moritani, S.; Tsuji, A. )

    1991-09-01

    The kinetics and mechanism of the transport of monocarboxylic acids (MCAs) were studied by using primary cultured bovine brain capillary endothelial cells. Concentration-dependent uptake of acetic acid was observed, and the kinetic parameters were estimated as follows: the Michaelis constant, Kt, was 3.41 {plus minus} 1.87 mM, the maximum uptake rate, Jmax, was 144.7 {plus minus} 55.7 nmol/mg of protein/min and the nonsaturable first-order rate constant, Kd, was 6.66 {plus minus} 1.98 microliters/mg of protein/min. At medium pH below 7.0, the uptake rate of (3H)acetic acid increased markedly with decreasing medium pH, whereas pH-independent uptake was observed in the presence of 10 mM acetic acid. An energy requirement for (3H)acetic acid uptake was also demonstrated, because metabolic inhibitors (2,4-dinitrophenol and rotenone) reduced significantly the uptake rate (P less than .05). Carbonylcyanide-p-trifluoro-methoxyphenylhydrazone, a protonophore, inhibited significantly the uptake of (3H)acetic acid at medium pH of 5.0 and 6.0, whereas 4,4{prime}-diisothiocyanostilben-2,2{prime}-disulfonic acid did not. Several MCAs inhibited significantly the uptake rate of (3H)acetic acid, whereas di- and tricarboxylic acids did not. The uptake of (3H)acetic acid was competitively inhibited by salicylic acid, with an inhibition constant, Ki, of 3.60 mM, suggesting a common transport system between acetic acid and salicylic acid. Moreover, at the medium pH of 7.4, salicylic acid and valproic acid inhibited significantly the uptake of (3H)acetic acid, demonstrating that the transport of MCA drugs could also be ascribed to the MCA transport system at the physiologic pH.

  13. Regulation of Monocarboxylic Acid Transporter 1 Trafficking by the Canonical Wnt/β-Catenin Pathway in Rat Brain Endothelial Cells Requires Cross-talk with Notch Signaling.

    PubMed

    Liu, Zejian; Sneve, Mary; Haroldson, Thomas A; Smith, Jeffrey P; Drewes, Lester R

    2016-04-01

    The transport of monocarboxylate fuels such as lactate, pyruvate, and ketone bodies across brain endothelial cells is mediated by monocarboxylic acid transporter 1 (MCT1). Although the canonical Wnt/β-catenin pathway is required for rodent blood-brain barrier development and for the expression of associated nutrient transporters, the role of this pathway in the regulation of brain endothelial MCT1 is unknown. Here we report expression of nine members of the frizzled receptor family by the RBE4 rat brain endothelial cell line. Furthermore, activation of the canonical Wnt/β-catenin pathway in RBE4 cells via nuclear β-catenin signaling with LiCl does not alter brain endothelialMct1mRNA but increases the amount of MCT1 transporter protein. Plasma membrane biotinylation studies and confocal microscopic examination of mCherry-tagged MCT1 indicate that increased transporter results from reduced MCT1 trafficking from the plasma membrane via the endosomal/lysosomal pathway and is facilitated by decreased MCT1 ubiquitination following LiCl treatment. Inhibition of the Notch pathway by the γ-secretase inhibitorN-[N-(3,5-difluorophenacetyl)-l-alanyl]-S-phenylglycinet-butyl ester negated the up-regulation of MCT1 by LiCl, demonstrating a cross-talk between the canonical Wnt/β-catenin and Notch pathways. Our results are important because they show, for the first time, the regulation of MCT1 in cerebrovascular endothelial cells by the multifunctional canonical Wnt/β-catenin and Notch signaling pathways.

  14. Aliphatic, Cyclic, and Aromatic Organic Acids, Vitamins, and Carbohydrates in Soil: A Review

    PubMed Central

    Vranova, Valerie; Rejsek, Klement; Formanek, Pavel

    2013-01-01

    Organic acids, vitamins, and carbohydrates represent important organic compounds in soil. Aliphatic, cyclic, and aromatic organic acids play important roles in rhizosphere ecology, pedogenesis, food-web interactions, and decontamination of sites polluted by heavy metals and organic pollutants. Carbohydrates in soils can be used to estimate changes of soil organic matter due to management practices, whereas vitamins may play an important role in soil biological and biochemical processes. The aim of this work is to review current knowledge on aliphatic, cyclic, and aromatic organic acids, vitamins, and carbohydrates in soil and to identify directions for future research. Assessments of organic acids (aliphatic, cyclic, and aromatic) and carbohydrates, including their behaviour, have been reported in many works. However, knowledge on the occurrence and behaviour of D-enantiomers of organic acids, which may be abundant in soil, is currently lacking. Also, identification of the impact and mechanisms of environmental factors, such as soil water content, on carbohydrate status within soil organic matter remains to be determined. Finally, the occurrence of vitamins in soil and their role in biological and biochemical soil processes represent an important direction for future research. PMID:24319374

  15. Aliphatic, cyclic, and aromatic organic acids, vitamins, and carbohydrates in soil: a review.

    PubMed

    Vranova, Valerie; Rejsek, Klement; Formanek, Pavel

    2013-11-10

    Organic acids, vitamins, and carbohydrates represent important organic compounds in soil. Aliphatic, cyclic, and aromatic organic acids play important roles in rhizosphere ecology, pedogenesis, food-web interactions, and decontamination of sites polluted by heavy metals and organic pollutants. Carbohydrates in soils can be used to estimate changes of soil organic matter due to management practices, whereas vitamins may play an important role in soil biological and biochemical processes. The aim of this work is to review current knowledge on aliphatic, cyclic, and aromatic organic acids, vitamins, and carbohydrates in soil and to identify directions for future research. Assessments of organic acids (aliphatic, cyclic, and aromatic) and carbohydrates, including their behaviour, have been reported in many works. However, knowledge on the occurrence and behaviour of D-enantiomers of organic acids, which may be abundant in soil, is currently lacking. Also, identification of the impact and mechanisms of environmental factors, such as soil water content, on carbohydrate status within soil organic matter remains to be determined. Finally, the occurrence of vitamins in soil and their role in biological and biochemical soil processes represent an important direction for future research.

  16. Aliphatic structure of humic acids; a clue to their origin

    USGS Publications Warehouse

    Hatcher, P.G.; Maciel, G.E.; Dennis, L.W.

    1981-01-01

    Nuclear magnetic resonance spectra (both 1H and 13C) of humic acids from diverse depositional environments indicate the presence of aromatic chemical structures, most likely derived from lignin of vascular plants, and complex, paraffinic structures, most likely derived from algal or microbial sources. The latter components account for a major fraction of humic acid structures in both terrestrial and aquatic environments, suggesting that algae or microbes play a large role in humification of organic remains from both systems. ?? 1981.

  17. Cellular distributions of monocarboxylate transporters: a review.

    PubMed

    Iwanaga, Toshihiko; Kishimoto, Ayuko

    2015-01-01

    Lactate and ketone bodies play important roles as alternative energy substrates, especially in conditions with a decreased utility of glucose. Short-chain fatty acids (acetate, propionate, and butyrate), produced by bacterial fermentation, supply most of the energy substrates in ruminants such as the cow and sheep. These monocarboxylates are transfered through the plasma membrane by proton-coupled monocarboxylate transporters (MCTs) and sodium-coupled MCTs (SMCTs). To reveal the metabolism and functional significance of monocarboxylates, the cellular localization of MCTs and SMCTs together with the expressed intensities holds great importance. This paper reviews the immunohistochemical localization of SMCTs and major MCT subtypes throughout the mammalian body. MCTs and SMCTs display a selective membrane-bound localization with porality. In contrast to the limited expression of SMCTs in the intestine and kidney, MCTs display a broader distribution pattern than GLUTs. The brain, kidney, placenta, and male genital tract express multiple subtypes of the MCT family. Determination of the cellular localization of MCTs is most controversial in the brain, possibly due to regional differences and the transcriptional modification of MCT proteins. Information on the localization of MCTs and SMCTs aids in understanding the nutrient absorption and metabolism throughout the mammalian body. In some cases, the body may use monocarboxylates as signal molecules, like hormones. PMID:26522146

  18. Electron ionization and dissociation of aliphatic amino acids

    NASA Astrophysics Data System (ADS)

    Papp, P.; Shchukin, P.; Kočíšek, J.; Matejčík, Š.

    2012-09-01

    We present experimental and theoretical study of electron ionization and dissociative ionization to the gas phase amino acids valine, leucine, and isoleucine. A crossed electron/molecular beams technique equipped with quadrupole mass analyzer has been applied to measure mass spectra and ion efficiency curves for formation of particular ions. From experimental data the ionization energies of the molecules and the appearance energies of the fragment ions were determined. Ab initio calculations (Density Functional Theory and G3MP2 methods) were performed in order to calculate the fragmentation paths and interpret the experimental data. The experimental ionization energies of parent molecules [P]+ 8.91 ± 0.05, 8.85 ± 0.05, and 8.79 ± 0.05 eV and G3MP2 ionization energies (adiabatic) of 8.89, 8.88, and 8.81 eV were determined for valine, leucine, and isoleucine, respectively, as well as the experimental and theoretical threshold energies for dissociative ionization channels. The comparison of experimental data with calculations resulted in identification of the ions as well as the neutral fragments formed in the dissociative reactions. Around 15 mass/charge ratio fragments were identified from the mass spectra by comparison of experimental appearance energies with calculated reaction enthalpies for particular dissociative reactions.

  19. Monocarboxylate transporter 1 is up-regulated in Caco-2 cells by the methionine precursor DL-2-hydroxy-(4-methylthio)butanoic acid.

    PubMed

    Martín-Venegas, Raquel; Brufau, M Teresa; Mañas-Cano, Oriol; Mercier, Yves; Nonis, Magalie K; Ferrer, Ruth

    2014-12-01

    The methionine precursor, DL-2-hydroxy-(4-methylthio)butanoic acid (HMTBA), is a synthetic source of dietary methionine, which is widely used as a poultry nutritional supplement. In the intestinal epithelium, HMTBA transport across the apical membrane is mediated by monocarboxylate transporter 1 (MCT1). The first step in biological utilisation of this methionine precursor is the stereospecific conversion of HMTBA to the corresponding keto acid. In the present study, the regulation of trans-epithelial HMTBA transport was investigated in Caco-2 cell monolayers. Differentiated Caco-2 cells were maintained under control conditions (apical compartment: 0.2 mmol/L L-methionine) or in a HMTBA-enriched medium (2 mmol/L HMTBA). The effect of culture on HMTBA transport was evaluated from apical and basolateral kinetic parameters. MCT1 and MCT4 immuno-localisation and gene expression were investigated by confocal microscopy and real-time quantitative RT-PCR, respectively. The results indicated that apical MCT1 was up-regulated by exposure to HMTBA (1.4-fold increase in Vmax without changes in Km). Moreover, total monolayer MCT1 immunoreactivity increased 1.8-fold in HMTBA-supplemented cultures, this effect mainly being localised at the apical membrane. Functional and immuno-localisation data suggest involvement of MCT1 and MCT4 in basolateral HMTBA transport, although, in this case, no effect was observed for HMTBA-enrichment. Molecular analysis confirmed MCT1 mRNA up-regulation (1.8-fold), with no effect on MCT4 mRNA expression. Thus, exposure to HMTBA up-regulates the trans-epithelial transport of this methionine precursor by increasing the expression and the transport capacity of apical MCT1. PMID:25447800

  20. Monocarboxylate transporter 1 is up-regulated in Caco-2 cells by the methionine precursor DL-2-hydroxy-(4-methylthio)butanoic acid.

    PubMed

    Martín-Venegas, Raquel; Brufau, M Teresa; Mañas-Cano, Oriol; Mercier, Yves; Nonis, Magalie K; Ferrer, Ruth

    2014-12-01

    The methionine precursor, DL-2-hydroxy-(4-methylthio)butanoic acid (HMTBA), is a synthetic source of dietary methionine, which is widely used as a poultry nutritional supplement. In the intestinal epithelium, HMTBA transport across the apical membrane is mediated by monocarboxylate transporter 1 (MCT1). The first step in biological utilisation of this methionine precursor is the stereospecific conversion of HMTBA to the corresponding keto acid. In the present study, the regulation of trans-epithelial HMTBA transport was investigated in Caco-2 cell monolayers. Differentiated Caco-2 cells were maintained under control conditions (apical compartment: 0.2 mmol/L L-methionine) or in a HMTBA-enriched medium (2 mmol/L HMTBA). The effect of culture on HMTBA transport was evaluated from apical and basolateral kinetic parameters. MCT1 and MCT4 immuno-localisation and gene expression were investigated by confocal microscopy and real-time quantitative RT-PCR, respectively. The results indicated that apical MCT1 was up-regulated by exposure to HMTBA (1.4-fold increase in Vmax without changes in Km). Moreover, total monolayer MCT1 immunoreactivity increased 1.8-fold in HMTBA-supplemented cultures, this effect mainly being localised at the apical membrane. Functional and immuno-localisation data suggest involvement of MCT1 and MCT4 in basolateral HMTBA transport, although, in this case, no effect was observed for HMTBA-enrichment. Molecular analysis confirmed MCT1 mRNA up-regulation (1.8-fold), with no effect on MCT4 mRNA expression. Thus, exposure to HMTBA up-regulates the trans-epithelial transport of this methionine precursor by increasing the expression and the transport capacity of apical MCT1.

  1. Aliphatic amidase of Rhodococcus rhodochrous PA-34: Purification, characterization and application in synthesis of acrylic acid.

    PubMed

    Thakur, Neerja; Kumar, Vijay; Sharma, Nirmal Kant; Thakur, Shikha; Bhalla, Tek Chand

    2016-01-01

    An intracellular aliphatic amide degrading inducible amidase produced by Rhodococcus rhodochrous PA-34 was characterized and acrylic acid synthesis from acrylamide was carried out using whole cell amidase. A bioprocess was developed at 50 ml fed batch reaction using 400 mM acrylamide feeding at an interval of 30 min resulted in the production of 4 g acrylic acid with volumetric and catalytic productivity of 80 g/l and 19 g/g/h respectively. The amidase of this organism had molecular weight of 40 kDa and was purified to 8.5 fold with 8% yield. This enzyme was active within the temperature range of 30 to 60 °C, with optimum temperature 45 °C and pH 7.5. The Vmax, Km, and kcat of purified amidase were calculated as 250 U/mg protein, 4.5 mM, and 166 sec-1 for acrylamide. The enzyme showed tolerance to metal chelating agent (EDTA) and was strongly inhibited by heavy metal ions Hg2+, Ag2+, Cu2+ and Co2+. R. rhodochrous PA-34 amidase preferentially hydrolyzed small aliphatic toxic amide such as acrylamide. Thus, the amidase of R. rhodochrous PA-34 is promising biocatalyst for the synthesis of industrially important acids and biodegradation of toxic amides. PMID:26667322

  2. Role of monocarboxylate transporters in drug delivery to the brain.

    PubMed

    Vijay, Nisha; Morris, Marilyn E

    2014-01-01

    Monocarboxylate transporters (MCTs) are known to mediate the transport of short chain monocarboxylates such as lactate, pyruvate and butyrate. Currently, fourteen members of this transporter family have been identified by sequence homology, of which only the first four members (MCT1- MCT4) have been shown to mediate the proton-linked transport of monocarboxylates. Another transporter family involved in the transport of endogenous monocarboxylates is the sodium coupled MCTs (SMCTs). These act as a symporter and are dependent on a sodium gradient for their functional activity. MCT1 is the predominant transporter among the MCT isoforms and is present in almost all tissues including kidney, intestine, liver, heart, skeletal muscle and brain. The various isoforms differ in terms of their substrate specificity and tissue localization. Due to the expression of these transporters in the kidney, intestine, and brain, they may play an important role in influencing drug disposition. Apart from endogenous short chain monocarboxylates, they also mediate the transport of exogenous drugs such as salicylic acid, valproic acid, and simvastatin acid. The influence of MCTs on drug pharmacokinetics has been extensively studied for γ-hydroxybutyrate (GHB) including distribution of this drug of abuse into the brain and the results will be summarized in this review. The physiological role of these transporters in the brain and their specific cellular localization within the brain will also be discussed. This review will also focus on utilization of MCTs as potential targets for drug delivery into the brain including their role in the treatment of malignant brain tumors.

  3. 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.

    PubMed

    Chiriac, Constantin I; Tanasa, Fulga; Onciu, Marioara

    2005-02-28

    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 degrees C) for 8-12 hours.

  4. Recommended Correlations for the Surface Tension of Aliphatic, Carboxylic, and Polyfunctional Organic Acids

    NASA Astrophysics Data System (ADS)

    Mulero, A.; Cachadiña, I.; Sanjuán, E. L.

    2016-09-01

    In previous papers, we have proposed specific correlations to reproduce the surface tension values for several sets of fluids and for wide ranges of temperatures. In this paper, we focus our attention on organic fatty (aliphatic, carboxylic, and polyfunctional) acids. We have taken into account the available data and values in the DIPPR and DETHERM databases and also Wohlfarth and Wohlfarth's (1997) book. In some cases we have also considered new data published elsewhere. All the data and values have been carefully filtered and subsequently fitted with the use of the model currently implemented in NIST's REFPROP program, calculating two or four adjustable coefficients for each fluid. As a result, we propose recommended correlations for 99 acids, providing mean absolute percentage deviations below 1.6% in all cases.

  5. Correlation between stabilities of uranyl ion complexes with various monocarboxylic acids and Hammett-Taft substituent constants

    SciTech Connect

    Poluektov, N.S.; Perfil'ev, V.A.; Meshkova, S.B.; Mishchenko, V.T.

    1987-01-01

    A correlation has been observed between the stabilities of uranyl ion complexes (1:1 composition) and the substituent inductive constants in formic and acetic acid derivatives. For substituents which are not directly involved in couples formation the parameters of the Hammett-Taft equation log K/sub 1/ = A + B have the following values: A = 1.311, B = -2.360. For substituents which form a coordination bond with the uranyl ion, A = 7.0077 and B = - 17.321. In the case of complexes formed between the uranyl ion and salicylic acid and its derivatives, there is a correlation between complex stability and sigma/sub m/ and sigma/sub p/ substituent constants for the meta- and para-positions, respectively (A = 12.72, B = -4.41).

  6. Fragmentation and dimerization of aliphatic amino acid films induced by vacuum ultraviolet irradiation

    NASA Astrophysics Data System (ADS)

    Tanaka, Masahito; Kaneko, Fusae; Koketsu, Toshiyuki; Nakagawa, Kazumichi; Yamada, Toru

    2008-10-01

    The chemical reaction of aliphatic amino acid, such as alanine (Ala) and leucine (Leu), in the solid phase induced by vacuum ultraviolet (VUV) irradiation was studied by high-performance liquid chromatography technique and mass spectroscopic method. Quantum efficiencies of dimerization of Ala in the solid phase obviously showed irradiated VUV wavelength dependence. The values of quantum efficiencies of formation of Ala dimer were determined to be 5.7×10-5, 1.3×10-3, and 2.4×10-4 for 208, 183, and 87 nm irradiation, respectively. VUV-induced fragment desorption from Ala and Leu films has also been examined by mass spectroscopic method. Observed mass spectra clearly indicated that both the deamination and decarboxylation reactions were common in both Ala and Leu films, and the dissociation of side chain occurred only in Leu film.

  7. Transition-metal-free visible-light photoredox catalysis at room-temperature for decarboxylative fluorination of aliphatic carboxylic acids by organic dyes.

    PubMed

    Wu, Xinxin; Meng, Chunna; Yuan, Xiaoqian; Jia, Xiaotong; Qian, Xuhong; Ye, Jinxing

    2015-07-28

    We report herein an efficient, general and green method for decarboxylative fluorination of aliphatic carboxylic acids. By using a transition-metal-free, organocatalytic photoredox system, the reaction of various aliphatic carboxylic acids with the Selectfluor reagent afforded the corresponding alkyl fluorides in satisfactory yields under visible light irradiation at room temperature.

  8. Gamma-irradiation stability of saturated and unsaturated aliphatic polyanhydrides--ricinoleic acid based polymers.

    PubMed

    Teomim, D; Mäder, K; Bentolila, A; Magora, A; Domb, A J

    2001-01-01

    The effect of terminal sterilization by gamma-irradiation on several ricinoleic acid based polyanhydrides was investigated. The following polymers were used: poly(ricinoleic acid maleate) [P(RAM)], poly(ricinoleic acid succinate) [P(RAS)], poly(hydroxy stearic acid succinate) [P(HSAS)], poly(hydroxy stearic acid maleate) [P(HSAM)], and their copolymers with sebacic acid. The polymers were irradiated with an absorbed dose of 2.5 or 10 Mrad by means of a 60Co source under dry ice or at room temperature. No differences were found between samples irradiated under dry ice and at room temperature. Polymers prepared from monomers containing maleate residues, which contain double bonds adjusted to the anhydride linkage along the polymer chain, decreased in molecular weight, became insoluble, and showed fast hydrolytic degradation. For example, p(RAM), p(HSAM), and their copolymers with sebacic acid decreased in Mw from about 10,000 to about 2000, and from about 30,000 to about 5000, respectively, while polymers based on RAS and HSAS remained stable. This phenomenon was explained by an anhydride interchange-self-depolymerization process of the unsaturated anhydride bonds induced by gamma-irradiation. This explanation was supported by the depolymerization of another class of polymers having an anhydride bond between two double bonds, fumaric acid anhydride polymers. The anhydride bond that lies between two double bonds was found to be more sensitive to gamma-irradiation. This anhydride bond may be cleaved to form two radicals that further react with aliphatic anhydride bonds along the polymer chain to form inter- and/or intracyclization products. PMID:11710004

  9. Aliphatic Hydrocarbons of Cladosporium resinae Cultured on Glucose, Glutamic Acid, and Hydrocarbons

    PubMed Central

    Walker, J. D.; Cooney, J. J.

    1973-01-01

    The carbon source markedly influenced the qualitative and quantitative composition of cellular hydrocarbons in Cladosporium resinae. Total lipid and hydrocarbon content was greater in cells grown on n-alkanes than in cells grown on glucose or glutamic acid. Glucose-grown cells contained a spectrum of aliphatic hydrocarbons from C7 to C36; pristane and n-hexadecane comprised 98% of the total. Cells grown on glutamic acid contained C7 to C23 hydrocarbons; n-tridecane, n-tetradecane, n-hexadecane, and pristane made up 74% of the total. n-Decane-grown cells yielded C8 to C32 compounds, and n-hexadecane (96%) was the major hydrocarbon. Cells grown on individual n-alkanes from C11 to C15 all contained C11 to C28 hydrocarbons, and cells grown on n-hexadecane contained C11 to C32 hydrocarbons. In n-undecane-grown cells, n-hexadecane and pristane made up 92% of the total, but in cells grown on C12 to C16 n-alkanes the major cellular hydrocarbon was the one on which the cells were grown. This suggests that cells cultured on n-alkanes of C12 or longer accumulate n-alkanes prior to oxidizing them. PMID:4762391

  10. Marsh plant response to metals: Exudation of aliphatic low molecular weight organic acids (ALMWOAs)

    NASA Astrophysics Data System (ADS)

    Rocha, A. Cristina S.; Almeida, C. Marisa R.; Basto, M. Clara P.; Vasconcelos, M. Teresa S. D.

    2016-03-01

    Metal exposure is known to induce the production and secretion of substances, such as aliphatic low molecular weight organic acids (ALMWOAs), into the rhizosphere by plant roots. Knowledge on this matter is extensive for soil plants but still considerably scarce regarding marsh plants roots adapted to high salinity media. Phragmites australis and Halimione portulacoides, two marsh plants commonly distributed in European estuarine salt marshes, were used to assess the response of roots of both species, in terms of ALMWOAs exudation, to Cu, Ni and Cd exposure (isolated and in mixture since in natural environment, they are exposed to mixture of metals). As previous studies were carried out in unrealistic and synthetic media, here a more natural medium was selected. Therefore, in vitro experiments were carried out, with specimens of both marsh plants, and in freshwater contaminated with two different Cu, Ni and Cd concentrations (individual metal and in mixture). Both marsh plants were capable of liberating ALMWOAs into the surrounding medium. Oxalic, citric and maleic acids were found in P. australis root exudate solutions and oxalic and maleic acids in H. portulacoides root exudate solutions. ALMWOA liberation by both plants was plant species and metal-dependent. For instance, Cu affected the exudation of oxalic acid by H. portulacoides and of oxalic and citric acids by P. australis roots. In contrast, Ni and Cd did not stimulate any specific response. Regarding the combination of all metals, H. portulacoides showed a similar response to that observed for Cu individually. However, in the P. australis case, at high metal concentration mixture, a synergetic effect led to the increase of oxalic acid levels in root exudate solution and to a decrease of citric acid liberation. A correlation between ALMWOAs exudation and metal accumulation could not be established. P. australis and H. portulacoides are considered suitable metal phytoremediators of estuarine impacted areas

  11. Direct enantioseparation of underivatized aliphatic 3-hydroxyalkanoic acids with a quinine-based zwitterionic chiral stationary phase.

    PubMed

    Ianni, Federica; Pataj, Zoltán; Gross, Harald; Sardella, Roccaldo; Natalini, Benedetto; Lindner, Wolfgang; Lämmerhofer, Michael

    2014-10-10

    While aliphatic 2-hydroxyalkanoic acids have been more or less successfully enantioseparated with various chiral stationary phases by HPLC and GC, analogous applications on underivatized aliphatic 3-hydroxyalkanoic acids are completely absent in the scientific literature. With the aim of closing this gap, the enantioseparation of 3-hydroxybutyric acid, 3-hydroxydecanoic acid and 3-hydroxymyristic acid has been performed with two ion-exchange type chiral stationary phases (CSPs): one containing the anion-exchange type tert-butyl carbamoyl quinine chiral selector motif (Chiralpak QN-AX), and the other carrying the new zwitterionic variant based on trans-(S,S)-2-aminocyclohexanesulfonic acid-derivatized quinine carbamate (Chiralpak ZWIX(+)) as the chiral selector and enantiodiscriminating element, respectively. The zwitterionic enantiorecognition material provided better results in terms of enantioselectivity and resolution compared to the anion-exchanger CSP at reduced retention times due to the intramolecular counterion effect imposed by the sulfonic acid moiety and its competition with the 3-hydroxyalkanoic acid analyte for ionic interaction at the quininium-anion exchanger site. It is thus recommended as the CSP of first choice for enantioseparations of the class of aliphatic 3-hydroxyalkanoic acids. With use of polar organic eluent composed of ACN/MeOH/AcOH - 95/5/0.05 (v/v/v), a good compromise in terms of analysis time and enantioresolution quality was accomplished. The major experimental variables have been investigated for optimization of the resolution and allowed to derive information on the enantiorecognition mechanism. Corresponding Chiralpak ZWIX(-), based on pseudo-enantiomeric selector derived from quinidine and trans-(R,R)-2-aminocyclohexanesulfonic acid with opposite configurations provided reversed enantiomer elution orders. It has further to be stressed that these separations can be obtained with mass spectrometry compatible mobile phases.

  12. Properties of Copolymers of Aspartic Acid and Aliphatic Dicarboxylic Acids Prepared by Reactive Extrusion

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aspartic acid may be prepared chemically or by the fermentation of carbohydrates. Currently, low molecular weight polyaspartic acids are prepared commercially by heating aspartic acid at high temperatures (greater than 220 degrees C) for several hours in the solid state. In an effort to develop a ...

  13. Analysis of. gamma. -radiolysis products of aqueous solutions of esters of aliphatic amino acids by the PMR method

    SciTech Connect

    Panin, V.I.; Sidorov, P.S.; Usatyi, A.F.

    1987-09-01

    The ..gamma..-radiolysis of aqueous solutions of methyl esters of aliphatic amino acids and peptides was investigated by the method of nuclear (proton) magnetic resonance (PMR). The resonance lines appearing in the PMR spectra of the irradiated systems were identified, and a conclusion was drawn about the molecular structure of the radiolysis products. The kinetics of the accumulation of radiolysis products was studied, and the values of their radiation yields were estimated.

  14. Kinetics of aluminum and sulfate release from forest soil by mono- and diprotic aliphatic acids

    SciTech Connect

    Evans, A. Jr.; Zelazny, L.W. )

    1990-06-01

    A batch equilibration study evaluated the influence of naturally occurring low-molecular-weight mono- and diprotic aliphatic acids on the rate of Al and SO{sub 4}{sup 2{minus}} release in a Cecil soil (Typic Hapludult). The authors adjusted the pH of the organic acids (OAs) and of the soil suspension (3.8% w/w) to pH 4.0 and allowed them to equilibrate thermally before the experiment. After rapid addition of OAs to the soil suspension, they took solution samples at various time intervals and analyzed for Al, SO{sub 4}{sup 2{minus}}, and OA concentration. The initial concentration of OA in suspension was 1 {times} 10{sup {minus}5} mol liter{sup {minus}1}. Both Al and SO{sub 4}{sup 2{minus}} release followed pseudo-first-order kinetics, whereas OA adsorption obeyed simple first-order kinetics. The rate of Al release (k{sub 1}) was more rapid for the diprotic OA treatment (20.4 {times} 10{sup {minus}8} mol s{sup {minus}1}), as was SO{sub 4}{sup 2{minus}} release (1.63 {times} 10{sup {minus}8} mol s{sup {minus}1}), compared to the monoprotic OA treatment. The rate of Al release varied inversely with OA chain length and the distance between -COOH functional groups. The addition of substituent -OH groups between the -COOH groups further reduced K{sub 1}. A similar trend was observed for the rate of SO{sub 4}{sup 2{minus}} release (k{sub 1}) into solution. Monoprotic OAs were more rapidly adsorbed to the particle surfaces than were diprotic OAs. The authors postulate that removal of Al and SO{sub 4}{sup 2{minus}} from solution occurs via selective mineral precipitation.

  15. Ion-Exclusion High-Performance Liquid Chromatography of Aliphatic Organic Acids Using a Surfactant-Modified C18 Column.

    PubMed

    Fasciano, Jennifer M; Mansour, Fotouh R; Danielson, Neil D

    2016-07-01

    Ion exclusion chromatography (IELC) of short chain aliphatic carboxylic acids is normally done using a cation exchange column under standard HPLC conditions but not in the ultra-HPLC (UHPLC) mode. A novel IELC method for the separation of this class of carboxylic acids by either HPLC or UHPLC utilizing a C18 column dynamically modified with sodium dodecyl sulfate has been developed. The sample capacity is estimated to be near 10 mM for a 20 µL injection or 0.2 µmol using a 150 × 4.6 mm column. The optimum mobile phase determined for three standard mixtures of organic acids is 1.84 mM sulfuric acid at pH 2.43 and a flow rate of 0.6 mL/min. Under optimized conditions, a HPLC separation of four aliphatic carboxylic acids such as tartaric, malonic, lactic and acetic can be achieved in under 4 min and in <2 min in the UHPLC mode at 2.1 mL/min. A variety of fruit juice and soft drink samples are analyzed. Stability of the column as measured by the retention order of maleic and fumaric acid is estimated to be ∼4,000 column volumes using HPLC and 600 by UHPLC. Reproducible chromatograms are achieved over at least a 2-month period. This study shows that the utility of a C18 column can be easily extended when needed to IELC under either standard or UHPLC conditions.

  16. Ion-Exclusion High-Performance Liquid Chromatography of Aliphatic Organic Acids Using a Surfactant-Modified C18 Column.

    PubMed

    Fasciano, Jennifer M; Mansour, Fotouh R; Danielson, Neil D

    2016-07-01

    Ion exclusion chromatography (IELC) of short chain aliphatic carboxylic acids is normally done using a cation exchange column under standard HPLC conditions but not in the ultra-HPLC (UHPLC) mode. A novel IELC method for the separation of this class of carboxylic acids by either HPLC or UHPLC utilizing a C18 column dynamically modified with sodium dodecyl sulfate has been developed. The sample capacity is estimated to be near 10 mM for a 20 µL injection or 0.2 µmol using a 150 × 4.6 mm column. The optimum mobile phase determined for three standard mixtures of organic acids is 1.84 mM sulfuric acid at pH 2.43 and a flow rate of 0.6 mL/min. Under optimized conditions, a HPLC separation of four aliphatic carboxylic acids such as tartaric, malonic, lactic and acetic can be achieved in under 4 min and in <2 min in the UHPLC mode at 2.1 mL/min. A variety of fruit juice and soft drink samples are analyzed. Stability of the column as measured by the retention order of maleic and fumaric acid is estimated to be ∼4,000 column volumes using HPLC and 600 by UHPLC. Reproducible chromatograms are achieved over at least a 2-month period. This study shows that the utility of a C18 column can be easily extended when needed to IELC under either standard or UHPLC conditions. PMID:27006111

  17. Contamination of aluminium oxide surfaces in ambient air investigated by FTIR MSR and TOF SIMS. Chemisorption of aliphatic carboxylic acids

    NASA Astrophysics Data System (ADS)

    Sondag, A. H. M.; Raas, M. C.; Van Velzen, P. N. T.

    1989-03-01

    Contamination in ambient air of freshly evaporated aluminium surfaces covered with a thin layer of native oxide has been studied using Fourier transform infrared multiple specular reflectance (FTIR MSR) and time-of-flight secondary ion mass spectrometry (TOF SIMS). The FTIR MSR experiments yield vibrational spectra than can be attributed to short-chain aliphatic carboxylic acids. Some reference spectra have been measured by FTIR MSR spectroscopy of samples prepared by chemisorption of formic, acetic, lactic, butyric and palmitic acids on oxidized aluminium and (in some cases) silver surfaces. From these data the major contaminant has to be the acetate ion. Saturation of the spectral intensities is observed within an hour after exposure to air. The TOF SIMS spectra confirm the conclusion with respect to the acetate ion. Mass peaks belonging to the formate, lactate and some inorganic anions are present in the TOF SIMS spectra.

  18. Monocarboxylate Transporter 1 Inhibitors as Potential Anticancer Agents

    PubMed Central

    2015-01-01

    Potent monocarboxylate transporter 1 inhibitors (MCT1) have been developed based on α-cyano-4-hydroxycinnamic acid template. Structure–activity relationship studies demonstrate that the introduction of p-N, N-dialkyl/diaryl, and o-methoxy groups into cyanocinnamic acid has maximal MCT1 inhibitory activity. Systemic toxicity studies in healthy ICR mice with few potent MCT1 inhibitors indicate normal body weight gains in treated animals. In vivo tumor growth inhibition studies in colorectal adenocarcinoma (WiDr cell line) in nude mice xenograft models establish that compound 27 exhibits single agent activity in inhibiting the tumor growth. PMID:26005533

  19. Synthesis of nanomagnetic fluids and their UV spectrophotometric response with aliphatic organic acids and 1st tier dendrimers

    NASA Astrophysics Data System (ADS)

    Pandya, Shivani R.; Singh, Man

    2016-04-01

    Synthesis of Magnetic nanoparticles were made using coprecipitation method on mixing Fe+3 and Fe+2 in 2:1 ratio with aqueous 8M NaOH which on heating at 90°C for 2 h has yielded 85% magnetic (Fe3O4) nanoparticles (MNPs), characterized by XRD, VSM, SEM, and HR-TEM. The formic acid (FA), oxalic acid (OA) and citric acid (CA), the series of aliphatic organic acids along with Trimesoyl 1, 3, 5 tridimethyl malonate (TTDMM), trimesoyl 1, 3, 5 tridiethyl malonate (TTDEM), trimesoyl 1, 3, 5 tridipropyl malonate (TTDPM), trimesoyl 1, 3, 5 tridibutyl malonate (TTDBM) and trimesoyl 1, 3, 5 tridihexyl malonate (TTDHM) 1st tier dendrimers were used separately for preparing nanomagnetic fluid. From 25 to 150 µM MNPs at an interval of 25 µM were dispersed in 150 µM of acids and dendrimers separately with DMSO. UV-VIS spectrophotometry showed a maximum MNPs dispersion with TTDMM against others and found to be most stable nanomagnetic fluid on account of capping type mechanism of acids.

  20. Enzymatic Polymerization of Furan-2,5-Dicarboxylic Acid-Based Furanic-Aliphatic Polyamides as Sustainable Alternatives to Polyphthalamides.

    PubMed

    Jiang, Yi; Maniar, Dina; Woortman, Albert J J; Alberda van Ekenstein, Gert O R; Loos, Katja

    2015-11-01

    Furan-2,5-dicarboxylic acid (FDCA)-based furanic-aliphatic polyamides can be used as promising sustainable alternatives to polyphthalamides (semiaromatic polyamides) and be applied as high performance materials with great commercial interest. In this study, poly(octamethylene furanamide) (PA8F), an analog to poly(octamethylene terephthalamide) (PA8T), is successfully produced via Novozym 435 (N435)-catalyzed polymerization, using a one-stage method in toluene and a temperature-varied two-stage method in diphenyl ether, respectively. The enzymatic polymerization results in PA8F with high weight-average molecular weight (M̅(w)) up to 54000 g/mol. Studies on the one-stage enzymatic polymerization in toluene indicate that the molecular weights of PA8F increase significantly with the concentration of N435; with an optimal reaction temperature of 90 °C. The temperature-varied, two-stage enzymatic polymerization in diphenyl ether yields PA8F with higher molecular weights, as compared to the one-stage procedure, at higher reaction temperatures. MALDI-ToF MS analysis suggests that eight end groups are present in the obtained PA8F: ester/amine, ester/ester, amine/amine, acid/amine, ester/acid, acid/acid, ester/amide, and no end groups (cyclic). Compared to PA8T, the obtained PA8F possesses a similar Tg and similar crystal structures, a comparable Td, but a lower Tm.

  1. Catalytic C-H bond activation at nanoscale Lewis acidic aluminium fluorides: H/D exchange reactions at aromatic and aliphatic hydrocarbons.

    PubMed

    Prechtl, Martin H G; Teltewskoi, Michael; Dimitrov, Anton; Kemnitz, Erhard; Braun, Thomas

    2011-12-16

    Nanoscopic amorphous Lewis acidic aluminium fluorides, such as aluminium chlorofluoride (ACF) and high-surface aluminium fluoride (HS-AlF(3)), are capable of activating C-H bonds of aliphatic hydrocarbons. H/D exchange reactions are catalysed under mild conditions (40 °C).

  2. Rainwater monocarboxylic and dicarboxylic acid concentrations in southeastern North Carolina, USA, as a function of air-mass back-trajectory

    NASA Astrophysics Data System (ADS)

    Brooks Avery, G.; Kieber, Robert J.; Witt, Melanie; Willey, Joan D.

    Eight organic acids were measured in 111 rain events occurring between September 1996 and May 1998 in Wilmington, North Carolina. Formic and acetic acids were the most abundant comprising approximately 75% of the total molar quantity of organic acids. The annual volume-weighted concentrations of organic acids in order of decreasing abundance in rainwater was formic (9.9 μM), acetic (7.3 μM), oxalic (1.8 μM), lactic (1.3 μM), succinic (1.0 μM), malonic (0.7 μM), pyruvic (0.3 μM), and maleic (0.1 μM), with methanesulfonic and glyoxylic acids usually below their detection limit. Growing season back-trajectory data provided strong evidence that terrestrial organic acid sources dominated over marine sources. Air mass back-trajectory analysis indicated that during the growing season air mass origin had a consistent impact on concentrations of rainwater organic acids. Rain with continental back-trajectories coming from the west had the highest concentrations of organic acids while two predominately marine back-trajectories had the lowest concentrations. Concentrations of organic acids in non-growing season rain did not display a consistent pattern indicating variability in sources. Seasonality of individual organic acids for specific back-trajectories was most pronounced in terrestrial back-trajectories and least in the marine back-trajectories indicating that seasonality in rainwater organic acid concentrations is driven by variations in terrestrial sources. Formic to acetic acid ratios (F:A), previously an indicator of terrestrial versus marine sources of these organic acids, were similar for all back-trajectories reflecting anthropogenic impacts on F:A locally and regionally. The ratios of malonic to succinic acids (M:S), also an indicator of sources for these acids, indicated direct anthropogenic sources for terrestrial back-trajectories and secondary processes for marine back-trajectories.

  3. Dual effects of aliphatic carboxylic acids on cresolase and catecholase reactions of mushroom tyrosinase.

    PubMed

    Gheibi, N; Saboury, A A; Haghbeen, K; Rajaei, F; Pahlevan, A A

    2009-10-01

    Catecholase and cresolase activities of mushroom tyrosinase (MT) were studied in presence of some n-alkyl carboxylic acid derivatives. Catecholase activity of MT achieved its optimal activity in presence of 1.0, 1.25, 2.0, 2.2 and 3.2 mM of pyruvic acid, acrylic acid, propanoic acid, 2-oxo-butanoic acid, and 2-oxo-octanoic acid, respectively. Contrarily, the cresolase activity of MT was inhibited by all type of the above acids. Propanoic acid caused an uncompetitive mode of inhibition (K(i)=0.14 mM), however, the pyruvic, acrylic, 2-oxo-butanoic and 2-oxo-octanoic acids showed a competitive manner of inhibition with the inhibition constants (K(i)) of 0.36, 0.6, 3.6 and 4.5 mM, respectively. So, it seems that, there is a physical difference in the docking of mono- and o-diphenols to the tyrosinase active site. This difference could be an essential determinant for the course of the catalytic cycle. Monophenols are proposed to bind only the oxyform of the tyrosinase. It is likely that the binding of acids occurs through their carboxylate group with one copper ion of the binuclear site. Thus, they could completely block the cresolase reaction, by preventing monophenol binding to the enzyme. From an allosteric point of view, n-alkyl acids may be involved in activation of MT catecholase reactions.

  4. Simultaneous and sensitive analysis of aliphatic carboxylic acids by ion-chromatography using on-line complexation with copper(II) ion.

    PubMed

    Kemmei, Tomoko; Kodama, Shuji; Yamamoto, Atsushi; Inoue, Yoshinori; Hayakawa, Kazuichi

    2015-01-01

    A new approach to ion chromatography is proposed to improve the UV detection of aliphatic carboxylic acids separated by anion-exchange chromatography. When copper(II) ion added to the mobile phase, it forms complexes with carboxylic acids that can be detected at 240 nm. The absorbance was found to increase with increasing copper(II) ion concentration. The retention times of α-hydroxy acids were also found to depend on the copper(II) ion concentration. Addition of acetonitrile to the mobile phase improved the separation of aliphatic carboxylic acids. The detection limits of the examined carboxylic acids (formate, glycolate, acetate, lactate, propionate, 3-hydroxypropionate, n-butyrate, isobutyrate, n-valerate, isovalerate, n-caproate) calculated at S/N=3 ranged from 0.06 to 3 μM. The detector signal was linear over three orders of magnitude of carboxylic acid concentration. The proposed method was successfully applied to analyze aliphatic carboxylic acids in rainwater and bread.

  5. Structure and properties of Al-MIL-53-ADP, a breathing MOF based on the aliphatic linker molecule adipic acid.

    PubMed

    Reinsch, Helge; Pillai, Renjith S; Siegel, Renée; Senker, Jürgen; Lieb, Alexandra; Maurin, Guillaume; Stock, Norbert

    2016-03-14

    The new aluminium based metal-organic framework [Al(OH)(O2C-C4H8-CO2)]·H2O denoted as Al-MIL-53-ADP-lp (lp stands for large pore) was synthesised under solvothermal conditions. This solid is an analogue of the archetypical aluminium terephthalate Al-MIL-53 based on the aliphatic single-chain linker molecule adipic acid (H2ADP, hexanedioic acid). In contrast to its aromatic counterparts, Al-MIL-53-ADP exhibits a structural breathing behaviour solely upon dehydration/rehydration. The crystal structure of the anhydrous compound denoted as Al-MIL-53-ADP-np (np stands for narrow pore) was determined by a combination of forcefield-based computations and Rietveld refinement of the powder X-ray diffraction data while the structure of the hydrated form Al-MIL-53-ADP-lp was derived computationally by a combination of force field based methods and Density Functional Theory calculations. Both structures were further supported by (1)H, (13)C and (27)Al high-resolution NMR MAS 1D data coupled again with simulations. Al-MIL-53-ADP was further characterised by means of vibrational spectroscopy, elemental analysis, thermogravimetry and water vapour sorption. PMID:26498663

  6. Aliphatic Hydrocarbons and Fatty Acids of Some Marine and Freshwater Microorganisms

    PubMed Central

    Oró, J.; Tornabene, T. G.; Nooner, D. W.; Gelpi, E.

    1967-01-01

    Gas chromatography and combined gas chromatography-mass spectrometry have been used to study the fatty acids and hydrocarbons of a bacterium from the Pacific Ocean, Vibrio marinus, a freshwater blue-green alga, Anacystis nidulans, and algal mat communities from the Gulf of Mexico. Both types of microorganisms (bacteria and algae) showed relatively simple hydrocarbon and fatty acid patterns, the hydrocarbons predominating in the region of C-17 and the fatty acids in the range of C-14 to C-18. The patterns of V. marinus were more comparable to those of the algal populations than to patterns reported for other bacteria. An incomplete correlation between fatty acids and hydrocarbons in both types of organisms was observed, making it difficult to accept the concept that the biosynthesis of hydrocarbons follows a simple fatty acid decarboxylation process. PMID:6025301

  7. Removal of aliphatic amino acids by hybrid organic inorganic layered compounds

    NASA Astrophysics Data System (ADS)

    Silverio, Fabiano; dos Reis, Márcio José; Tronto, Jairo; Valim, João Barros

    2007-04-01

    Amino acids have been extensively used in several processes of the pharmaceutical and food industries. Treatments for the recovery and reuse of the wastewaters generated from these processes are few and little known. This work aims at studying the influence of variables like temperature, pH and ionic strength on the adsorption of the amino acids Asp and Glu, contained in aqueous solutions, on layered double hydroxides of the Mg-Al-CO 3-LDH system. The adsorption experiments were performed at two different temperatures (298 and 310 K), two different pH values (7.0 and 10.0), and two ionic strength conditions (with or without the addition of NaCl). The adsorption isotherms exhibited similar profiles under the various conditions studied: an increase in temperature as well as an increase in the pH value decreased the amount of adsorbed amino acid while an increase in the ionic strength increased Asp and Glu adsorption. The PXRD analysis showed that the diffractograms obtained before and after the adsorption of amino acids have a similar pattern. The FT-IR spectra of the adsorbed material presented specific bands, which are related to the amino acids. The concentration range varied up to the anion solubility product and the extraction rate lay between 2.7 and 23.4% at higher equilibrium concentrations, showing that Mg-Al-CO 3-LDH is efficient at removing the amino acids from the aqueous medium.

  8. Generation of aliphatic acid anions and carbon dioxide by hydrous pyrolysis of crude oils

    USGS Publications Warehouse

    Kharaka, Y.K.; Lundegard, P.D.; Ambats, G.; Evans, William C.; Bischoff, J.L.

    1993-01-01

    Two crude oils with relatively high (0.60 wt%) and low (0.18 wt%) oxygen contents were heated in the presence of water in gold-plated reactors at 300??C for 2348 h. The high-oxygen oil was also heated at 200??C for 5711 h. The compositions of aqueous organic acid anions of the oils and of the headspace gases were monitored inn order to investigate the distribution of organic acids that can be generated from liquid petroleum. The oil with higher oxygen content generated about five times as much organic anions as the other oil. The dominant organic anions produced were acetate, propionate and butyrate. Small amounts of formate, succinate, methyl succinate and oxalate were also produced. The dominant oxygen-containing product was CO2, as has been observed in similar studies on the hydrous pyrolysis of kerogen. These results indicate that a significant portion (10-30%) of organic acid anions reported i be generated by thermal alteration of oils in reservoir rocks. The bulk of organic acid anions present in formation waters, however, is most likely generated by thermal alteration of kerogen in source rocks. Kerogen is more abundant than oil in sedimentary basins and the relative yields of organic acid anions reported from the hydrous pyrolysis of kerogen are much higher than the yields obtained for the two oils. ?? 1993.

  9. Lipid bilayer permeation of aliphatic amine and carboxylic acid drugs: rates of insertion, translocation and dissociation from MD simulations.

    PubMed

    Oruç, Tuğçe; Küçük, Sami Emre; Sezer, Deniz

    2016-09-21

    Aliphatic amines (AAs) and carboxylic acids (CAs) constitute the two most commonly occurring chemical groups among orally active drugs [Manallack, et al., ChemMedChem, 2013, 8, 242]. Here, we aim to rationalize this observation in terms of molecular properties that are essential for drug bioavailability. To this end, the permeation of the AA drug dyclonine and the CA drug 4-phenylbutyrate through a lipid bilayer is studied with molecular dynamics (MD) simulations. Permeability coefficients for the neutral and ionized forms of these drugs are calculated using the inhomogeneous solubility-diffusion model. To draw conclusions about other AA and CA drugs, the permeability coefficient is expressed as a sum over contributions from drug insertion into, translocation across, and dissociation from the lipid bilayer. Simple but general expressions for each of these separate steps are obtained and validated against the MD simulations of dyclonine and phenylbutyrate. We conclude that the neutral forms of most AA and CA drugs have large permeability coefficients (>1 cm s(-1)), while their ionized forms ensure solubility in aqueous environments. Thus, a physicochemical rationale for the reported abundance of AAs and CAs among drugs is provided.

  10. Lipid bilayer permeation of aliphatic amine and carboxylic acid drugs: rates of insertion, translocation and dissociation from MD simulations.

    PubMed

    Oruç, Tuğçe; Küçük, Sami Emre; Sezer, Deniz

    2016-09-21

    Aliphatic amines (AAs) and carboxylic acids (CAs) constitute the two most commonly occurring chemical groups among orally active drugs [Manallack, et al., ChemMedChem, 2013, 8, 242]. Here, we aim to rationalize this observation in terms of molecular properties that are essential for drug bioavailability. To this end, the permeation of the AA drug dyclonine and the CA drug 4-phenylbutyrate through a lipid bilayer is studied with molecular dynamics (MD) simulations. Permeability coefficients for the neutral and ionized forms of these drugs are calculated using the inhomogeneous solubility-diffusion model. To draw conclusions about other AA and CA drugs, the permeability coefficient is expressed as a sum over contributions from drug insertion into, translocation across, and dissociation from the lipid bilayer. Simple but general expressions for each of these separate steps are obtained and validated against the MD simulations of dyclonine and phenylbutyrate. We conclude that the neutral forms of most AA and CA drugs have large permeability coefficients (>1 cm s(-1)), while their ionized forms ensure solubility in aqueous environments. Thus, a physicochemical rationale for the reported abundance of AAs and CAs among drugs is provided. PMID:27539552

  11. Design, Synthesis, EPR-Studies and Conformational Bias of Novel Spin-Labeled DCC-Analogues for the Highly Regioselective Labeling of Aliphatic and Aromatic Carboxylic Acids.

    PubMed

    Gölz, Jan Philipp; NejatyJahromy, Yaser; Bauer, Mirko; Muhammad, Ashraf; Schnakenburg, Gregor; Grimme, Stefan; Schiemann, Olav; Menche, Dirk

    2016-07-01

    Novel types of spin-labeled N,N'-dicyclohexylcarbodiimides (DCC) are reported that bear a 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) residue on one side and different aromatic and aliphatic cyclohexyl analogues on the other side of the diimide core. These readily available novel reagents add efficiently to aliphatic and aromatic carboxylic acids, forming two possible spin-labeled amide derivatives with different radical distances of the resulting amide. The addition of aromatic DCC analogues proceeds with excellent selectivity, giving amides where the carboxylic acid is exclusively connected to the aromatic residue, while little or no selectivity was observed for the aliphatic congeners. The usefulness of these adducts in structural studies was demonstrated by EPR (electron paramagnetic resonance) measurements of biradical adducts of biphenyl-4,4'-dicarboxylic acids. These analyses also reveal high degrees of conformational bias for aromatic DCC derivatives, which further underlines the powerfulness of these novel reagents. This observation was further corroborated by quantum chemical calculations, giving a detailed understanding of the structural dynamics, while detailed information on the solid state structure of all novel reagents was obtained by X-ray structure analyses.

  12. Design, Synthesis, EPR-Studies and Conformational Bias of Novel Spin-Labeled DCC-Analogues for the Highly Regioselective Labeling of Aliphatic and Aromatic Carboxylic Acids.

    PubMed

    Gölz, Jan Philipp; NejatyJahromy, Yaser; Bauer, Mirko; Muhammad, Ashraf; Schnakenburg, Gregor; Grimme, Stefan; Schiemann, Olav; Menche, Dirk

    2016-07-01

    Novel types of spin-labeled N,N'-dicyclohexylcarbodiimides (DCC) are reported that bear a 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) residue on one side and different aromatic and aliphatic cyclohexyl analogues on the other side of the diimide core. These readily available novel reagents add efficiently to aliphatic and aromatic carboxylic acids, forming two possible spin-labeled amide derivatives with different radical distances of the resulting amide. The addition of aromatic DCC analogues proceeds with excellent selectivity, giving amides where the carboxylic acid is exclusively connected to the aromatic residue, while little or no selectivity was observed for the aliphatic congeners. The usefulness of these adducts in structural studies was demonstrated by EPR (electron paramagnetic resonance) measurements of biradical adducts of biphenyl-4,4'-dicarboxylic acids. These analyses also reveal high degrees of conformational bias for aromatic DCC derivatives, which further underlines the powerfulness of these novel reagents. This observation was further corroborated by quantum chemical calculations, giving a detailed understanding of the structural dynamics, while detailed information on the solid state structure of all novel reagents was obtained by X-ray structure analyses. PMID:27272435

  13. Reactions of charged phenyl radicals with aliphatic amino acids in the gas phase.

    PubMed

    Huang, Yiqun; Guler, Leo; Heidbrink, Jenny; Kenttämaa, Hilkka

    2005-03-23

    Gas-phase reactivity of five differently substituted positively charged phenyl radicals was examined toward six amino acids by using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR). The reactivity of the radicals studied was determined by the electrophilicity of the radical, which can be characterized by the radical's electron affinity (EA). The larger the electron affinity of the radical, the higher the overall reaction rate. In addition to the expected H-atom abstraction, several unprecedented reaction pathways were observed, including NH2 abstraction, SH abstraction, and SCH3 abstraction. These reaction pathways dominate for the most electrophilic radicals, and they may not follow radical but rather nucleophilic addition-elimination mechanisms. Hydrogen abstraction from glycine was also investigated theoretically. The results indicate that hydrogen abstraction from alphaC of glycine is both kinetically and thermodynamically favored over the NH2 group. The ordering of transition state energies for hydrogen abstraction from the alphaC and NH2 groups was found to reflect the radicals' EA ordering.

  14. Transepithelial transport of aliphatic carboxylic acids studied in Madin Darby canine kidney (MDCK) cell monolayers.

    PubMed

    Cho, M J; Adson, A; Kezdy, F J

    1990-04-01

    Transport of 14C-labeled acetic, propionic (PA), butyric, valeric, heptanoic (HA), and octanoic (OA) acids across the Madin Darby canine kidney (MDCK) epithelial cell monolayer grown on a porous polycarbonate membrane was studied in Hanks' balanced salt solution (HBSS) at 37 degrees C in both apical-to-basolateral and basolateral-to-apical directions. At micromolar concentrations of solutes, metabolic decomposition was significant as evidenced by [14C]CO2 production during the OA transport. The apparent permeability (Pe) indicates that as lipophilicity increases, diffusion across the "unstirred" boundary layer becomes rate limiting. In support of this notion, transport of OA and HA was enhanced by agitation, showed an activation energy of 3.7 kcal/mol for OA, and resulted in identical Pe values for both transport directions. Analysis of Pe changes with varying alkyl chain length resulted in a delta G of -0.68 +/- 0.09 kcal/mol for -CH2-group transfer from an aqueous phase to the MDCK cells. When the intercellular tight junctions were opened by the divalent chelator EGTA in Ca2+/Mg2(+)-free HBSS, transport of the fluid-phase marker Lucifer yellow greatly increased because of paracellular leakage. PA transport also showed a significant increase, but OA transport was independent of EGTA. Although albumin also undergoes paracellular transport in the presence of EGTA and OA binds strongly to albumin, OA transport in EGTA solution was unchanged by albumin. These observations indicate that transmembrane transport is the major mechanism for lipophilic substances. The present study, together with earlier work on the transport of polar substances, shows that the MDCK cell monolayer is an excellent model of the transepithelial transport barrier.

  15. Transepithelial transport of aliphatic carboxylic acids studied in Madin Darby canine kidney (MDCK) cell monolayers

    SciTech Connect

    Cho, M.J.; Adson, A.; Kezdy, F.J. )

    1990-04-01

    Transport of 14C-labeled acetic, propionic (PA), butyric, valeric, heptanoic (HA), and octanoic (OA) acids across the Madin Darby canine kidney (MDCK) epithelial cell monolayer grown on a porous polycarbonate membrane was studied in Hanks' balanced salt solution (HBSS) at 37{degrees}C in both apical-to-basolateral and basolateral-to-apical directions. At micromolar concentrations of solutes, metabolic decomposition was significant as evidenced by (14C)CO2 production during the OA transport. The apparent permeability (Pe) indicates that as lipophilicity increases, diffusion across the unstirred boundary layer becomes rate limiting. In support of this notion, transport of OA and HA was enhanced by agitation, showed an activation energy of 3.7 kcal/mol for OA, and resulted in identical Pe values for both transport directions. Analysis of Pe changes with varying alkyl chain length resulted in a delta G of -0.68 +/- 0.09 kcal/mol for -CH2-group transfer from an aqueous phase to the MDCK cells. When the intercellular tight junctions were opened by the divalent chelator EGTA in Ca2+/Mg2(+)-free HBSS, transport of the fluid-phase marker Lucifer yellow greatly increased because of paracellular leakage. PA transport also showed a significant increase, but OA transport was independent of EGTA. Although albumin also undergoes paracellular transport in the presence of EGTA and OA binds strongly to albumin, OA transport in EGTA solution was unchanged by albumin. These observations indicate that transmembrane transport is the major mechanism for lipophilic substances. The present study, together with earlier work on the transport of polar substances, shows that the MDCK cell monolayer is an excellent model of the transepithelial transport barrier.

  16. A base-mediated self-propagative Lossen rearrangement of hydroxamic acids for the efficient and facile synthesis of aromatic and aliphatic primary amines.

    PubMed

    Ohtsuka, Naoya; Okuno, Moriaki; Hoshino, Yujiro; Honda, Kiyoshi

    2016-10-14

    A variety of aromatic and aliphatic hydroxamic acids were converted to the corresponding primary amines via base-mediated rearrangement. This rearrangement could proceed with less than 1 equiv. of K2CO3 in polar solvents under thermal conditions with no external reagents. This rearrangement has several features including no external activating agents needed for promoting the rearrangement, less than one equivalent of a base is sufficient for the reaction, and a clean reaction in which only carbon dioxide is produced as a by-product. A self-propagating mechanism via an isocyanate intermediate is proposed and elementary reaction steps, namely, chain propagation reactions are supported by experiments. PMID:27605448

  17. Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C-N Bond Formation from Nonactivated Aliphatic Carboxylic Acids.

    PubMed

    Liu, Zhao-Jing; Lu, Xi; Wang, Guan; Li, Lei; Jiang, Wei-Tao; Wang, Yu-Dong; Xiao, Bin; Fu, Yao

    2016-08-01

    Copper-catalyzed directed decarboxylative amination of nonactivated aliphatic carboxylic acids is described. This intramolecular C-N bond formation reaction provides efficient access to the synthesis of pyrrolidine and piperidine derivatives as well as the modification of complex natural products. Moreover, this reaction presents excellent site-selectivity in the C-N bond formation step through the use of directing group. Our work can be considered as a big step toward controllable radical decarboxylative carbon-heteroatom cross-coupling. PMID:27439145

  18. A base-mediated self-propagative Lossen rearrangement of hydroxamic acids for the efficient and facile synthesis of aromatic and aliphatic primary amines.

    PubMed

    Ohtsuka, Naoya; Okuno, Moriaki; Hoshino, Yujiro; Honda, Kiyoshi

    2016-10-14

    A variety of aromatic and aliphatic hydroxamic acids were converted to the corresponding primary amines via base-mediated rearrangement. This rearrangement could proceed with less than 1 equiv. of K2CO3 in polar solvents under thermal conditions with no external reagents. This rearrangement has several features including no external activating agents needed for promoting the rearrangement, less than one equivalent of a base is sufficient for the reaction, and a clean reaction in which only carbon dioxide is produced as a by-product. A self-propagating mechanism via an isocyanate intermediate is proposed and elementary reaction steps, namely, chain propagation reactions are supported by experiments.

  19. Peptidyl prolyl isomerase Pin1-inhibitory activity of D-glutamic and D-aspartic acid derivatives bearing a cyclic aliphatic amine moiety.

    PubMed

    Nakagawa, Hidehiko; Seike, Suguru; Sugimoto, Masatoshi; Ieda, Naoya; Kawaguchi, Mitsuyasu; Suzuki, Takayoshi; Miyata, Naoki

    2015-12-01

    Pin1 is a peptidyl prolyl isomerase that specifically catalyzes cis-trans isomerization of phosphorylated Thr/Ser-Pro peptide bonds in substrate proteins and peptides. Pin1 is involved in many important cellular processes, including cancer progression, so it is a potential target of cancer therapy. We designed and synthesized a novel series of Pin1 inhibitors based on a glutamic acid or aspartic acid scaffold bearing an aromatic moiety to provide a hydrophobic surface and a cyclic aliphatic amine moiety with affinity for the proline-binding site of Pin1. Glutamic acid derivatives bearing cycloalkylamino and phenylthiazole groups showed potent Pin1-inhibitory activity comparable with that of known inhibitor VER-1. The results indicate that steric interaction of the cyclic alkyl amine moiety with binding site residues plays a key role in enhancing Pin1-inhibitory activity.

  20. Aquaporins with anion/monocarboxylate permeability: mechanisms, relevance for pathogen–host interactions

    PubMed Central

    Rambow, Janis; Wu, Binghua; Rönfeldt, Deike; Beitz, Eric

    2014-01-01

    Classically, aquaporins are divided based on pore selectivity into water specific, orthodox aquaporins and solute-facilitating aquaglyceroporins, which conduct, e.g., glycerol and urea. However, more aquaporin-passing substrates have been identified over the years, such as the gasses ammonia and carbon dioxide or the water-related hydrogen peroxide. It became apparent that not all aquaporins clearly fit into one of only two subfamilies. Furthermore, certain aquaporins from both major subfamilies have been reported to conduct inorganic anions, such as chloride, or monoacids/monocarboxylates, such as lactic acid/lactate. Here, we summarize the findings on aquaporin anion transport, analyze the pore layout of such aquaporins in comparison to prototypical non-selective anion channels, monocarboxylate transporters, and formate–nitrite transporters. Finally, we discuss in which scenarios anion conducting aquaporins may be of physiological relevance. PMID:25225485

  1. Tissue-specific expression of monocarboxylate transporters during fasting in mice.

    PubMed

    Schutkowski, Alexandra; Wege, Nicole; Stangl, Gabriele I; König, Bettina

    2014-01-01

    Monocarboxylates such as pyruvate, lactate and ketone bodies are crucial for energy supply of all tissues, especially during energy restriction. The transport of monocarboxylates across the plasma membrane of cells is mediated by monocarboxylate transporters (MCTs). Out of 14 known mammalian MCTs, six isoforms have been functionally characterized to transport monocarboxylates and short chain fatty acids (MCT1-4), thyroid hormones (MCT8, -10) and aromatic amino acids (MCT10). Knowledge on the regulation of the different MCT isoforms is rare. In an attempt to get more insights in regulation of MCT expression upon energy deprivation, we carried out a comprehensive analysis of tissue specific expression of five MCT isoforms upon 48 h of fasting in mice. Due to the crucial role of peroxisome proliferator-activated receptor (PPAR)-α as a central regulator of energy metabolism and as known regulator of MCT1 expression, we included both wildtype (WT) and PPARα knockout (KO) mice in our study. Liver, kidney, heart, small intestine, hypothalamus, pituitary gland and thyroid gland of the mice were analyzed. Here we show that the expression of all examined MCT isoforms was markedly altered by fasting compared to feeding. Expression of MCT1, MCT2 and MCT10 was either increased or decreased by fasting dependent on the analyzed tissue. MCT4 and MCT8 were down-regulated by fasting in all examined tissues. However, PPARα appeared to have a minor impact on MCT isoform regulation. Due to the fundamental role of MCTs in transport of energy providing metabolites and hormones involved in the regulation of energy homeostasis, we assumed that the observed fasting-induced adaptations of MCT expression seem to ensure an adequate energy supply of tissues during the fasting state. Since, MCT isoforms 1-4 are also necessary for the cellular uptake of drugs, the fasting-induced modifications of MCT expression have to be considered in future clinical care algorithms. PMID:25390336

  2. Use of a polystyrene-divinylbenzene-based weakly acidic cation-exchange resin column and propionic acid as an eluent in ion-exclusion/adsorption chromatography of aliphatic carboxylic acids and ethanol in food samples.

    PubMed

    Mori, Masanobu; Hironaga, Takahiro; Kajiwara, Hiroe; Nakatani, Nobutake; Kozaki, Daisuke; Itabashi, Hideyuki; Tanaka, Kazuhiko

    2011-01-01

    We developed an ion-exclusion/adsorption chromatography (IEAC) method employing a polystyrene-divinylbenzene-based weakly acidic cation-exchange resin (PS-WCX) column with propionic acid as the eluent for the simultaneous determination of multivalent aliphatic carboxylic acids and ethanol in food samples. The PS-WCX column well resolved mono-, di-, and trivalent carboxylic acids in the acidic eluent. Propionic acid as the eluent gave a higher signal-to-noise ratio, and enabled sensitive conductimetric detection of analyte acids. We found the optimal separation condition to be the combination of a PS-WCX column and 20-mM propionic acid. Practical applicability of the developed method was confirmed by using a short precolumn with a strongly acidic cation-exchange resin in the H(+)-form connected before the separation column; this was to remove cations from food samples by converting them to hydrogen ions. Consequently, common carboxylic acids and ethanol in beer, wine, and soy sauce were successfully separated by the developed method.

  3. Immunocytochemical expression of monocarboxylate transporters in the human visual cortex at midgestation.

    PubMed

    Fayol, Laurence; Baud, Olivier; Monier, Anne; Pellerin, Luc; Magistretti, Pierre; Evrard, Philippe; Verney, Catherine

    2004-01-31

    Lactate and the other monocarboxylates are a major energy source for the developing brain. We investigated the immunocytochemical expression of two monocarboxylate transporters, MCT1 and MCT2, in the human visual cortex between 13 and 26 post-ovulatory weeks. We used immunoperoxidase and immunofluorescence techniques to determine whether these transporters co-localized with markers for blood vessels (CD34), neurons (microtubule-associated protein 2 [MAP2], SMI 311), radial glia (vimentin), or astrocytes (glial fibrillary acidic protein [GFAP], S100beta protein). MCT1 immunoreactivity was visible in blood vessel walls as early as the 13th week of gestation mainly in the cortical plate and subplate. At this stage, less than 10% of vessels in the ventricular layer expressed MCT1, whereas all blood vessels walls showed this immunoreactivity at the 26th gestational week. Starting at the 19th week of gestation, sparse MCT1 positive cell bodies were detected, some of them co-localized with MAP2 immunoreactivity. MCT2 immunoreactivity was noted in astrocytic cell bodies from week 19 and spread subsequently to the astrocyte end-feet in contact with blood vessels. MCTs immunoreactivities were most marked in the subplate and deep cortical plate, where the most differentiated neurons were located. Our findings suggest that monocarboxylate trafficking between vessels (MCT1), astrocytes (MCT2) and some postmitotic neurons (MCT1) could develop gradually toward 20 gestational weeks (g.w.). These data suggest that lactate or other monocarboxylates could represent a significant energy source for the human visual cortex at this early stage. PMID:14757520

  4. Mixed ligand complexes of Cu(II)-2-(2-pyridyl)-benzimidazole and aliphatic or aromatic dicarboxylic acids: Synthesis, characterization and biological activity

    NASA Astrophysics Data System (ADS)

    El-Sherif, Ahmed A.; Jeragh, Bakir J. A.

    2007-11-01

    The synthesis and structural characterization of mixed ligand complexes derived from 2-(2-pyridyl)-benzimidazole (PBI) (1ry ligand) and aliphatic or aromatic dicarboxylic acids (2ry ligand) are reported. Cu(II) complexes were characterized on the bases of their elemental analyses, IR, ESR and thermal analyses. The elemental analysis indicated the formation of mixed ligand complexes in a mole ratio 1:1:1 (Cu:L 1:L 2), L 1 = PBI and L 2 = oxalic acid, phthalic acid or malonic acid. IR spectra showed that PBI acts as a neutral bidentate coordinated to the Cu(II) via the pyridyl and imidazolyl nitrogen atoms. The dicarboxylic acids are bidentate with monodentate carboxylate groups. Thermal decomposition study of complexes was monitored by thermogravimetric (TG) and derivative thermogravimetric (DTG) analysis in N 2 atmosphere. The decomposition course and steps were analysed and the activation parameters of the nonisothermal decomposition were calculated from the TG curves and discussed. The isolated metal chelates were screened for their antimicrobial activities and the results are reported, discussed and compared with some known antibiotics.

  5. Influence of season and salinity on the exudation of aliphatic low molecular weight organic acids (ALMWOAs) by Phragmites australis and Halimione portulacoides roots

    NASA Astrophysics Data System (ADS)

    Rocha, A. Cristina S.; Almeida, C. Marisa R.; Basto, M. Clara P.; Vasconcelos, M. Teresa S. D.

    2015-01-01

    Plant roots have the ability to produce and secrete substances, such as aliphatic low molecular weight organic acids (ALMWOAs), into the rhizosphere. This phenomenon occurs for several purposes, for instance, the detoxification of pollutants. Nevertheless, knowledge about the exudation of such substances from marsh plants roots is still scarce. This work aimed at studying: 1) the ability of marsh plants, freshly collected in estuarine marshes, to liberate ALMWOAs into the surrounding medium and 2) the influence of the physiological cycle of these plants on the exudation of those substances. In vitro experiments were carried out, in different seasons, with Phragmites australis and Halimione portulacoides (two marsh plants widely distributed in Europe). Root exudates were collected in freshwater to which plant specimens, in different physiological stages, were exposed. Both marsh plants were capable of liberating oxalic and citric acids into the surrounding medium. Formic acid was also released by P. australis roots and acetic acid by H. portulacoides. There was a seasonal effect on the liberation of ALMWOAs by both plant roots. Marked changes were registered in the nature and levels of the ALMWOAs liberated and such changes depended upon the season in which the specimens were collected. In growing season, a significantly higher liberation of oxalic and citric acids (and acetic acid but only in H. portulacoides case) was observed. For P. australis, formic acid was only found in the decaying stage (autumn and winter). The nature of the medium (in particular, salinity) was a feature conditioning the exudation of ALMWOAs. Both plants were shown to contribute for the presence of ALMWOAs in marsh rhizosediments (some ALMWOAs were found in pore waters extracted). The nature and extent of this contribution will be however dependent upon plants' physiological stage, in addition to plant species. Therefore, these features should be taken into consideration in the event of

  6. Synergistic effects in solvent-extraction systems based on alkylsalicylic acids. I. Extraction of trivalent rare-earth metals in the presence of aliphatic amides

    SciTech Connect

    Preston, J.S.; Preez, A.C. du

    1995-07-01

    Aliphatic carboxylic acid amides were found to cause synergistic shifts in the pH{sub 50} values for the extraction of the trivalent rare-earth metals from chloride media by solutions of alkylsalicylic acids in xylene. For the different types of amide examined, the synergistic shifts for the extraction of neodymium by 3,5-diisopropylsalicylic acid (DIPSA) generally decrease in the order: R.CO.NR{sub 2}` > R.CO.NHR` > R.CO.NH{sub 2}, where R and R` are alkyl groups. With the N,N-dialkyl amides (R.CO.NR{sub 2}`) and the N-alkyl amides (R.CO.NHR`), the extent of the synergistic effect decreases with increasing chain-branching in either of the alkyl groups R and R`. For additions to 0.25 M alkylsalicylic acid, the synergistic effect increases with concentrations of up to 0.1 M amide, and decreases with higher concentrations. The extent of the synergistic shift produced by a given amide, as well as the separation in pH{sub 50} values from lanthanum to lutetium, increases with increasing steric bulk of the alkylsalicylic acid used. The separations between adjacent lanthanides are too small to be of any practical interest, however. Measurement of the solubility of salicylic acids (HA) in xylene containing various amounts of N,N-dialkyl amide (L) indicate that essentially complete formation of the HA.L adduct takes place. Treatment of metal-distribution data by slope analysis, and measurement of the solubility of the neodymium-DIPSA complex in xylene in the presence of amide suggest that the mixed-ligand complex has the stoichiometry NdA{sub 3}L{sub 2}. 18 refs., 6 figs., 3 refs.

  7. Monocarboxylate Transporters and Lactate Metabolism in Equine Athletes: A Review

    PubMed Central

    Pösö, AR

    2002-01-01

    Lactate is known as the end product of anaerobic glycolysis, a pathway that is of key importance during high intensity exercise. Instead of being a waste product lactate is now regarded as a valuable substrate that significantly contributes to the energy production of heart, noncontracting muscles and even brain. The recent cloning of monocarboxylate transporters, a conserved protein family that transports lactate through biological membranes, has given a new insight into the role of lactate in whole body metabolism. This paper reviews current literature on lactate and monocarboxylate transporters with special reference to horses. PMID:12173504

  8. Use of iron monocarboxylates in the two-step preparation of poly(ester-urethane)s.

    PubMed

    Stolt, M; Hiltunen, K; Södergård, A

    2001-01-01

    Five different iron monocarboxylates were used as catalysts in the two-step preparation route of lactic acid based poly(ester-urethane)s (PEU). In the first step, a hydroxyl-terminated poly(lactic acid) prepolymer was prepared, which in the second step was linked with 1,6-hexamethylene diisocyanate. The resulting polymers were characterized by titration, size exclusion chromatography, differential scanning calorimetry, and nuclear magnetic resonance spectroscopy, and the mechanical properties were tested as well. Iron monocarboxylates proved to be efficient catalysts in the preparation of a hydroxyl-terminated prepolymer (lowest acid number obtained: 0.08). The same catalyst systems proved also to be highly efficient in the linking step yielding a high molar mass PEU. Semicrystalline PEUs could be prepared at 160 and 180 degrees C by using the iron acetate of different oxidation state. PEU prepared at 200 degrees C was amorphous, which could be related to racemization during the polycondensation. By using the fluorinated iron acetate amorphous PEUs was prepared at all reaction temperatures. The molar mass of the prepolymers and the PEUs increased as a function of the polycondensation temperature for all catalysts used. The highest weight-average molar masses (M(w)) were obtained by using the fluorinated iron acetate. PMID:11777398

  9. Enrichment of aliphatic, alicyclic and aromatic acids by oil-degrading bacteria isolated from the rhizosphere of plants growing in oil-contaminated soil from Kazakhstan.

    PubMed

    Mikolasch, Annett; Omirbekova, Anel; Schumann, Peter; Reinhard, Anne; Sheikhany, Halah; Berzhanova, Ramza; Mukasheva, Togzhan; Schauer, Frieder

    2015-05-01

    Three microbial strains were isolated from the rhizosphere of alfalfa (Medicago sativa), grass mixture (Festuca rubra, 75 %; Lolium perenne, 20 %; Poa pratensis, 10 %), and rape (Brassica napus) on the basis of their high capacity to use crude oil as the sole carbon and energy source. These isolates used an unusually wide spectrum of hydrocarbons as substrates (more than 80), including n-alkanes with chain lengths ranging from C12 to C32, monomethyl- and monoethyl-substituted alkanes (C12-C23), n-alkylcyclo alkanes with alkyl chain lengths from 4 to 18 carbon atoms, as well as substituted monoaromatic and diaromatic hydrocarbons. These three strains were identified as Gordonia rubripertincta and Rhodococcus sp. SBUG 1968. During their transformation of this wide range of hydrocarbon substrates, a very large number of aliphatic, alicyclic, and aromatic acids was detected, 44 of them were identified by GC/MS analyses, and 4 of them are described as metabolites for the first time. Inoculation of plant seeds with these highly potent bacteria had a beneficial effect on shoot and root development of plants which were grown on oil-contaminated sand. PMID:25592733

  10. Enrichment of aliphatic, alicyclic and aromatic acids by oil-degrading bacteria isolated from the rhizosphere of plants growing in oil-contaminated soil from Kazakhstan.

    PubMed

    Mikolasch, Annett; Omirbekova, Anel; Schumann, Peter; Reinhard, Anne; Sheikhany, Halah; Berzhanova, Ramza; Mukasheva, Togzhan; Schauer, Frieder

    2015-05-01

    Three microbial strains were isolated from the rhizosphere of alfalfa (Medicago sativa), grass mixture (Festuca rubra, 75 %; Lolium perenne, 20 %; Poa pratensis, 10 %), and rape (Brassica napus) on the basis of their high capacity to use crude oil as the sole carbon and energy source. These isolates used an unusually wide spectrum of hydrocarbons as substrates (more than 80), including n-alkanes with chain lengths ranging from C12 to C32, monomethyl- and monoethyl-substituted alkanes (C12-C23), n-alkylcyclo alkanes with alkyl chain lengths from 4 to 18 carbon atoms, as well as substituted monoaromatic and diaromatic hydrocarbons. These three strains were identified as Gordonia rubripertincta and Rhodococcus sp. SBUG 1968. During their transformation of this wide range of hydrocarbon substrates, a very large number of aliphatic, alicyclic, and aromatic acids was detected, 44 of them were identified by GC/MS analyses, and 4 of them are described as metabolites for the first time. Inoculation of plant seeds with these highly potent bacteria had a beneficial effect on shoot and root development of plants which were grown on oil-contaminated sand.

  11. Synthesis of aliphatic esters of cinnamic acid as potential lipophilic antioxidants catalyzed by lipase B from Candida antarctica.

    PubMed

    Jakovetić, Sonja M; Jugović, Branimir Z; Gvozdenović, Milica M; Bezbradica, Dejan I; Antov, Mirjana G; Mijin, Dušan Z; Knežević-Jugović, Zorica D

    2013-08-01

    Immobilized lipase from Candida antarctica (Novozyme 435) was tested for the synthesis of various phenolic acid esters (ethyl and n-butyl cinnamate, ethyl p-coumarate and n-butyl p-methoxycinnamate). The second-order kinetic model was used to mathematically describe the reaction kinetics and to compare present processes quantitatively. It was found that the model agreed well with the experimental data. Further, the effect of alcohol type on the esterification of cinnamic acid was investigated. The immobilized lipase showed more ability to catalyze the synthesis of butyl cinnamate. Therefore, the process was optimized for the synthesis of butyl cinnamate as a function of solvent polarity (logP) and amount of biocatalyst. The highest ester yield of 60.7 % was obtained for the highest enzyme concentration tested (3 % w/w), but the productivity was for 34 % lower than the corresponding value obtained for the enzyme concentration of 1 % (w/w). The synthesized esters were purified, identified, and screened for antioxidant activities. Both DPPH assay and cyclic voltammetry measurement have shown that cinnamic acid esters have better antioxidant properties than cinnamic acid itself.

  12. Structural and spectroscopic properties of an aliphatic boronic acid studied by combination of experimental and theoretical methods

    NASA Astrophysics Data System (ADS)

    Cyrański, Michał K.; Jezierska, Aneta; Klimentowska, Paulina; Panek, Jarosław J.; Żukowska, GraŻyna Z.; Sporzyński, Andrzej

    2008-03-01

    Boronic acids have emerged as one of the most useful class of organoboron molecules, with application in synthesis, catalysis, analytical chemistry, supramolecular chemistry, biology, and medicine. In this study, the structural and spectroscopic properties of n-butylboronic acid were investigated using experimental and theoretical approaches. X-ray crystallography method provided structural information on the studied compound in the solid state. Infrared and Raman spectroscopy served as tools for the data collection on vibrational modes of the analyzed system. Car-Parrinello molecular dynamics simulations in solid state were carried out at 100 and 293K to investigate an environmental and temperature influence on molecular properties of the n-butylboronic acid. Analysis of interatomic distances of atoms involved in the intermolecular hydrogen bond was performed to study the proton motion in the crystal. Subsequently, Fourier transform of autocorrelation functions of atomic velocities and dipole moment was applied to study the vibrational properties of the compound. In addition, the inclusion of quantum nature of proton motion was performed for O-H stretching vibrational mode by application of the envelope method for intermolecular hydrogen-bonded system. The second part of the computational study consists of simulations performed in vacuo. Monomeric and dimeric forms of the n-butylboronic acid were investigated using density functional theory and Møller-Plesset second-order perturbation method. The basis set superposition error was estimated. Finally, atoms in molecules (AIM) theory was applied to study electron density topology and properties of the intermolecular hydrogen bond. Successful reproduction of the molecular properties of the n-butylboronic acid by computational methodologies, presented in the manuscript, indicates the way for future studies of large boron-containing organic systems of importance in biology or materials science.

  13. Structural and spectroscopic properties of an aliphatic boronic acid studied by combination of experimental and theoretical methods.

    PubMed

    Cyrański, Michał K; Jezierska, Aneta; Klimentowska, Paulina; Panek, Jarosław J; Zukowska, Grazyna Z; Sporzyński, Andrzej

    2008-03-28

    Boronic acids have emerged as one of the most useful class of organoboron molecules, with application in synthesis, catalysis, analytical chemistry, supramolecular chemistry, biology, and medicine. In this study, the structural and spectroscopic properties of n-butylboronic acid were investigated using experimental and theoretical approaches. X-ray crystallography method provided structural information on the studied compound in the solid state. Infrared and Raman spectroscopy served as tools for the data collection on vibrational modes of the analyzed system. Car-Parrinello molecular dynamics simulations in solid state were carried out at 100 and 293 K to investigate an environmental and temperature influence on molecular properties of the n-butylboronic acid. Analysis of interatomic distances of atoms involved in the intermolecular hydrogen bond was performed to study the proton motion in the crystal. Subsequently, Fourier transform of autocorrelation functions of atomic velocities and dipole moment was applied to study the vibrational properties of the compound. In addition, the inclusion of quantum nature of proton motion was performed for O-H stretching vibrational mode by application of the envelope method for intermolecular hydrogen-bonded system. The second part of the computational study consists of simulations performed in vacuo. Monomeric and dimeric forms of the n-butylboronic acid were investigated using density functional theory and Moller-Plesset second-order perturbation method. The basis set superposition error was estimated. Finally, atoms in molecules (AIM) theory was applied to study electron density topology and properties of the intermolecular hydrogen bond. Successful reproduction of the molecular properties of the n-butylboronic acid by computational methodologies, presented in the manuscript, indicates the way for future studies of large boron-containing organic systems of importance in biology or materials science. PMID:18376948

  14. Microbial degradation of aliphatic and aliphatic-aromatic co-polyesters.

    PubMed

    Shah, Aamer Ali; Kato, Satoshi; Shintani, Noboru; Kamini, Numbi Ramudu; Nakajima-Kambe, Toshiaki

    2014-04-01

    Biodegradable plastics (BPs) have attracted much attention since more than a decade because they can easily be degraded by microorganisms in the environment. The development of aliphatic-aromatic co-polyesters has combined excellent mechanical properties with biodegradability and an ideal replacement for the conventional nondegradable thermoplastics. The microorganisms degrading these polyesters are widely distributed in various environments. Although various aliphatic, aromatic, and aliphatic-aromatic co-polyester-degrading microorganisms and their enzymes have been studied and characterized, there are still many groups of microorganisms and enzymes with varying properties awaiting various applications. In this review, we have reported some new microorganisms and their enzymes which could degrade various aliphatic, aromatic, as well as aliphatic-aromatic co-polyesters like poly(butylene succinate) (PBS), poly(butylene succinate)-co-(butylene adipate) (PBSA), poly(ε-caprolactone) (PCL), poly(ethylene succinate) (PES), poly(L-lactic acid) (PLA), poly(3-hydroxybutyrate) and poly(3-hydoxybutyrate-co-3-hydroxyvalterate) (PHB/PHBV), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(butylene adipate-co-terephthalate (PBAT), poly(butylene succinate-co-terephthalate) (PBST), and poly(butylene succinate/terephthalate/isophthalate)-co-(lactate) (PBSTIL). The mechanism of degradation of aliphatic as well as aliphatic-aromatic co-polyesters has also been discussed. The degradation ability of microorganisms against various polyesters might be useful for the treatment and recycling of biodegradable wastes or bioremediation of the polyester-contaminated environments.

  15. Distribution and sources of aliphatic hydrocarbons and fatty acids in surface sediments of a tropical estuary south west coast of India (Cochin estuary).

    PubMed

    Gireeshkumar, T R; Deepulal, P M; Chandramohanakumar, N

    2015-03-01

    Surface sediments samples from the Cochin estuary were measured for elemental, stable isotopic and molecular biomarkers (aliphatic hydrocarbons and fatty acids) to study the sources and distribution of sedimentary organic matter. Concentrations of total organic carbon (TOC), total nitrogen (TN) and stable isotopic ratios of carbon (δ(13)C) ranged from 0.62 to 2.74 %, 0.09 to 0.25 % and -27.5 to 21.7 ‰, respectively. Sedimentary n-alkanes ranged from 6.03 to 43.23 μg g(-1) with an average of 16.79 μg g(-1), while total fatty acids varied from 22.55 to 440.69 μg g(-1). The TOC/TN ratios and δ(13)C suggest a mixture of marine- and terrestrial-derived organic matter in the surface sediments with increasing contributions from marine-derived organic matter towards the seaward side. Long-chain n-alkanes derived from higher plants predominated the inner part of the estuary, while short-chain n-alkanes derived from planktonic sources predominated the bar mouth region. The even carbon preference of the C12-C22 n-alkanes may refer to the direct biogenic contribution from bacteria, fungi and yeast species and to the potential direct petroleum inputs. The presence of odd mid-chain n-alkanes in the sediments indicates the organic matter inputs from submerged and floating macrophytes (water hyacinth). Various molecular indices such as carbon preference index, terrestrial to aquatic ratio, average chain length and the ratios of mid-chain n-alkanes support the aforementioned inferences. The high contribution of odd and branched chain fatty acids along with very low contribution of polyunsaturated fatty acids, suggest the effective utilisation of algae-derived organic matter by bacteria and the effective recycling of labile organic matter in whole settling and deposition processes. The distributional variability of n-alkanes and fatty acids reveals the preferential utilisation of marine-derived organic matter and the selective preservation of terrestrial

  16. The enzymatic activities of the Escherichia coli basic aliphatic amino acid decarboxylases exhibit a pH zone of inhibition.

    PubMed

    Kanjee, Usheer; Gutsche, Irina; Ramachandran, Shaliny; Houry, Walid A

    2011-11-01

    The stringent response regulator ppGpp has recently been shown by our group to inhibit the Escherichia coli inducible lysine decarboxylase, LdcI. As a follow-up to this observation, we examined the mechanisms that regulate the activities of the other four E. coli enzymes paralogous to LdcI: the constitutive lysine decarboxylase LdcC, the inducible arginine decarboxylase AdiA, the inducible ornithine decarboxylase SpeF, and the constitutive ornithine decarboxylase SpeC. LdcC and SpeC are involved in cellular polyamine biosynthesis, while LdcI, AdiA, and SpeF are involved in the acid stress response. Multiple mechanisms of regulation were found for these enzymes. In addition to LdcI, LdcC and SpeC were found to be inhibited by ppGpp; AdiA activity was found to be regulated by changes in oligomerization, while SpeF and SpeC activities were regulated by GTP. These findings indicate the presence of multiple mechanisms regulating the activity of this important family of decarboxylases. When the enzyme inhibition profiles are analyzed in parallel, a "zone of inhibition" between pH 6 and pH 8 is observed. Hence, the data suggest that E. coli utilizes multiple mechanisms to ensure that these decarboxylases remain inactive around neutral pH possibly to reduce the consumption of amino acids at this pH. PMID:21957966

  17. The enzymatic activities of the Escherichia coli basic aliphatic amino acid decarboxylases exhibit a pH zone of inhibition.

    PubMed

    Kanjee, Usheer; Gutsche, Irina; Ramachandran, Shaliny; Houry, Walid A

    2011-11-01

    The stringent response regulator ppGpp has recently been shown by our group to inhibit the Escherichia coli inducible lysine decarboxylase, LdcI. As a follow-up to this observation, we examined the mechanisms that regulate the activities of the other four E. coli enzymes paralogous to LdcI: the constitutive lysine decarboxylase LdcC, the inducible arginine decarboxylase AdiA, the inducible ornithine decarboxylase SpeF, and the constitutive ornithine decarboxylase SpeC. LdcC and SpeC are involved in cellular polyamine biosynthesis, while LdcI, AdiA, and SpeF are involved in the acid stress response. Multiple mechanisms of regulation were found for these enzymes. In addition to LdcI, LdcC and SpeC were found to be inhibited by ppGpp; AdiA activity was found to be regulated by changes in oligomerization, while SpeF and SpeC activities were regulated by GTP. These findings indicate the presence of multiple mechanisms regulating the activity of this important family of decarboxylases. When the enzyme inhibition profiles are analyzed in parallel, a "zone of inhibition" between pH 6 and pH 8 is observed. Hence, the data suggest that E. coli utilizes multiple mechanisms to ensure that these decarboxylases remain inactive around neutral pH possibly to reduce the consumption of amino acids at this pH.

  18. Isoquercitrin Esters with Mono- or Dicarboxylic Acids: Enzymatic Preparation and Properties

    PubMed Central

    Vavříková, Eva; Langschwager, Fanny; Jezova-Kalachova, Lubica; Křenková, Alena; Mikulová, Barbora; Kuzma, Marek; Křen, Vladimír; Valentová, Kateřina

    2016-01-01

    A series of isoquercitrin (quercetin-3-O-β-d-glucopyranoside) esters with mono- or dicarboxylic acids was designed to modulate hydro- and lipophilicity and biological properties. Esterification of isoquercitrin was accomplished by direct chemoenzymatic reaction using Novozym 435 (lipase from Candida antarctica), which accepted C5- to C12-dicarboxylic acids; the shorter ones, such as oxalic (C2), malonic (C3), succinic (C4) and maleic (C4) acids were not substrates of the lipase. Lipophilicity of monocarboxylic acid derivatives, measured as log P, increased with the chain length. Esters with glutaric and adipic acids exhibited hydrophilicity, and the dodecanedioic acid hemiester was more lipophilic. All derivatives were less able to reduce Folin–Ciocalteau reagent (FCR) and scavenge DPPH (1,1-diphenyl-2-picrylhydrazyl) than isoquercitrin; ABTS (2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid)) radical-scavenging activity was comparable. Dodecanoate and palmitate were the least active in FCR and ABTS scavenging; dodecanoate and hemiglutarate were the strongest DPPH scavengers. In contrast, most derivatives were much better inhibitors of microsomal lipoperoxidation than isoquercitrin; butyrate and hexanoate were the most efficient. Anti-lipoperoxidant activity of monocarboxylic derivatives, except acetates, decreased with increasing aliphatic chain. The opposite trend was noted for dicarboxylic acid hemiesters, isoquercitrin hemidodecanedioate being the most active. Overall, IQ butyrate, hexanoate and hemidodecanedioate are the most promising candidates for further studies. PMID:27338349

  19. Isoquercitrin Esters with Mono- or Dicarboxylic Acids: Enzymatic Preparation and Properties.

    PubMed

    Vavříková, Eva; Langschwager, Fanny; Jezova-Kalachova, Lubica; Křenková, Alena; Mikulová, Barbora; Kuzma, Marek; Křen, Vladimír; Valentová, Kateřina

    2016-01-01

    A series of isoquercitrin (quercetin-3-O-β-d-glucopyranoside) esters with mono- or dicarboxylic acids was designed to modulate hydro- and lipophilicity and biological properties. Esterification of isoquercitrin was accomplished by direct chemoenzymatic reaction using Novozym 435 (lipase from Candida antarctica), which accepted C₅- to C12-dicarboxylic acids; the shorter ones, such as oxalic (C₂), malonic (C₃), succinic (C₄) and maleic (C₄) acids were not substrates of the lipase. Lipophilicity of monocarboxylic acid derivatives, measured as log P, increased with the chain length. Esters with glutaric and adipic acids exhibited hydrophilicity, and the dodecanedioic acid hemiester was more lipophilic. All derivatives were less able to reduce Folin-Ciocalteau reagent (FCR) and scavenge DPPH (1,1-diphenyl-2-picrylhydrazyl) than isoquercitrin; ABTS (2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid)) radical-scavenging activity was comparable. Dodecanoate and palmitate were the least active in FCR and ABTS scavenging; dodecanoate and hemiglutarate were the strongest DPPH scavengers. In contrast, most derivatives were much better inhibitors of microsomal lipoperoxidation than isoquercitrin; butyrate and hexanoate were the most efficient. Anti-lipoperoxidant activity of monocarboxylic derivatives, except acetates, decreased with increasing aliphatic chain. The opposite trend was noted for dicarboxylic acid hemiesters, isoquercitrin hemidodecanedioate being the most active. Overall, IQ butyrate, hexanoate and hemidodecanedioate are the most promising candidates for further studies. PMID:27338349

  20. Controlled-release fertilizer prepared using a biodegradable aliphatic copolyester of poly(butylene succinate) and dimerized fatty acid.

    PubMed

    Lubkowski, Krzysztof; Smorowska, Aleksandra; Grzmil, Barbara; Kozłowska, Agnieszka

    2015-03-18

    The preparation and characterization of a controlled-release multicomponent (NPK) fertilizer with the coating layer consisting of a biodegradable copolymer of poly(butylene succinate) and a butylene ester of dilinoleic acid (PBS/DLA) is reported. The morphology and structure of the resulting polymer-coated materials and the thickness of the covering layers were examined using X-ray diffraction and scanning electron microscopy coupled with energy dispersive X-ray analysis. The mechanical properties of these materials were determined with a strength-testing machine. Nutrient release was measured in water using spectrophotometry, potentiometry, and conductivity methods. The results of the nutrient release experiments from these polymer-coated materials were compared with the requirements for controlled-release fertilizers. A conceptual model is presented describing the mechanism of nutrient release from the materials prepared in this study. This model is based on the concentrations of mineral components inside the water-penetrated fertilizer granules, the diffusion properties of the nutrients in water, and a diffusion coefficient through the polymer layer. The experimental kinetic data on nutrient release were interpreted using the sigmoidal model equation developed in this study. PMID:25715823

  1. Controlled-release fertilizer prepared using a biodegradable aliphatic copolyester of poly(butylene succinate) and dimerized fatty acid.

    PubMed

    Lubkowski, Krzysztof; Smorowska, Aleksandra; Grzmil, Barbara; Kozłowska, Agnieszka

    2015-03-18

    The preparation and characterization of a controlled-release multicomponent (NPK) fertilizer with the coating layer consisting of a biodegradable copolymer of poly(butylene succinate) and a butylene ester of dilinoleic acid (PBS/DLA) is reported. The morphology and structure of the resulting polymer-coated materials and the thickness of the covering layers were examined using X-ray diffraction and scanning electron microscopy coupled with energy dispersive X-ray analysis. The mechanical properties of these materials were determined with a strength-testing machine. Nutrient release was measured in water using spectrophotometry, potentiometry, and conductivity methods. The results of the nutrient release experiments from these polymer-coated materials were compared with the requirements for controlled-release fertilizers. A conceptual model is presented describing the mechanism of nutrient release from the materials prepared in this study. This model is based on the concentrations of mineral components inside the water-penetrated fertilizer granules, the diffusion properties of the nutrients in water, and a diffusion coefficient through the polymer layer. The experimental kinetic data on nutrient release were interpreted using the sigmoidal model equation developed in this study.

  2. CCN activity of aliphatic amine secondary aerosol

    NASA Astrophysics Data System (ADS)

    Tang, X.; Price, D.; Praske, E.; Vu, D.; Purvis-Roberts, K.; Silva, P. J.; Cocker, D. R., III; Asa-Awuku, A.

    2014-01-01

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, κ ≤ 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N2O5 (source of nitrate radical, NO3), contains less volatile compounds than the primary aliphatic amine (BA) aerosol. TMA + N2O5 form semi-volatile organics in low RH conditions that have κ ~ 0.20, indicative of slightly soluble organic material. As RH increases, several inorganic amine salts are formed as a result of acid-base reactions. The CCN activity of the humid TMA-N2O5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. Higher CCN activity (κ > 0.3) was also observed for humid BA+N2O5 aerosols compared with dry aerosol (κ ~ 0.2), as a result of the formation of inorganic salts such as NH4NO3 and butylamine nitrate (C4H11N · HNO3). Compared with TMA, BA+N2O5 reactions produce more volatile aerosols. The BA+N2O5 aerosol products under humid experiments were found to be very sensitive to the temperature within the stream-wise continuous flow thermal gradient CCN counter. The CCN counter, when set above a 21 °C temperature difference, evaporates BA+N2O5 aerosol formed at RH ≥ 30%; κ ranges from 0.4 to 0.7 and is dependent on the instrument supersaturation (ss) settings. The aerosol behaves non-ideally, hence simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems κ ranges from 0.2 < κ < 0.7. This work indicates that

  3. Self-assembly in solvates of 2,4-diamino-6-(4-methyl- phenyl)-1,3,5-triazine and in its molecular adducts with some aliphatic dicarboxylic acids

    NASA Astrophysics Data System (ADS)

    Nandy, Purnendu; Nayak, Amrita; Biswas, Sharmita Nandy; Pedireddi, V. R.

    2016-03-01

    Solid state structures of 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 1, in the form of methanol and dimethylsulfoxide (DMSO) solvates, as well as supramolecular assemblies of 1 with various aliphatic dicarboxylic acids, oxalic (a), malonic (b), succinic (c), glutaric (d) and adipic (e) have been reported. Analysis of the assemblies has been carried out by single crystal X-ray diffraction and thermal methods. Triazine 1 yields anhydrous molecular adducts with acids a-d, upon co-crystallization either from CH3OH and DMSO solvents. However acid e gives anhydrous adduct from DMSO solvent, while it gives a methanol adduct from CH3OH. Structure determination reveals that molecular adducts 1a, 1d and 1e are in a 2:1 ratio of 1 and the corresponding acid. However the ratio is 1:1, in 1b, perhaps due to the involvement of one of the acid groups in the intramolecular hydrogen bonding and in adduct 1c the ratio observed is 3:2. Structural features in all these assemblies have been rationalised in terms of various recognition patterns formed between the acceptor and donor groups. A noteworthy feature is that -COOH groups in acid a establish interaction with 1 through amino groups, while such interactions are observed to be through hetero -N atoms in case of the acids b-e.

  4. Anaerobic digestion of aliphatic polyesters.

    PubMed

    Šmejkalová, Pavla; Kužníková, Veronika; Merna, Jan; Hermanová, Soňa

    2016-01-01

    Anaerobic processes for the treatment of plastic materials waste represent versatile and effective approach in environmental protection and solid waste management. In this work, anaerobic biodegradability of model aliphatic polyesters, poly(L-lactic acid) (PLA), and poly(ɛ-caprolactone) (PCL), in the form of powder and melt-pressed films with varying molar mass, was studied. Biogas production was explored in batch laboratory trials at 55 ± 1°C under a nitrogen atmosphere. The inoculum used was thermophilic digested sludge (total solids concentration of 2.9%) from operating digesters at the Central Waste Water Treatment Plant in Prague, Czech Republic. Methanogenic biodegradation of PCLs typically yielded from 54 to 60% of the theoretical biogas yield. The biodegradability of PLAs achieved from 56 to 84% of the theoretical value. High biogas yield (up to 677 mL/g TS) with high methane content (more than 60%), comparable with conventionally processed materials, confirmed the potential of polyester samples for anaerobic treatment in the case of their exploitation in agriculture or as a packaging material in the food industry.

  5. Anaerobic digestion of aliphatic polyesters.

    PubMed

    Šmejkalová, Pavla; Kužníková, Veronika; Merna, Jan; Hermanová, Soňa

    2016-01-01

    Anaerobic processes for the treatment of plastic materials waste represent versatile and effective approach in environmental protection and solid waste management. In this work, anaerobic biodegradability of model aliphatic polyesters, poly(L-lactic acid) (PLA), and poly(ɛ-caprolactone) (PCL), in the form of powder and melt-pressed films with varying molar mass, was studied. Biogas production was explored in batch laboratory trials at 55 ± 1°C under a nitrogen atmosphere. The inoculum used was thermophilic digested sludge (total solids concentration of 2.9%) from operating digesters at the Central Waste Water Treatment Plant in Prague, Czech Republic. Methanogenic biodegradation of PCLs typically yielded from 54 to 60% of the theoretical biogas yield. The biodegradability of PLAs achieved from 56 to 84% of the theoretical value. High biogas yield (up to 677 mL/g TS) with high methane content (more than 60%), comparable with conventionally processed materials, confirmed the potential of polyester samples for anaerobic treatment in the case of their exploitation in agriculture or as a packaging material in the food industry. PMID:27191559

  6. Pyruvate fuels mitochondrial respiration and proliferation of breast cancer cells: effect of monocarboxylate transporter inhibition.

    PubMed

    Diers, Anne R; Broniowska, Katarzyna A; Chang, Ching-Fang; Hogg, Neil

    2012-06-15

    Recent studies have highlighted the fact that cancer cells have an altered metabolic phenotype, and this metabolic reprogramming is required to drive the biosynthesis pathways necessary for rapid replication and proliferation. Specifically, the importance of citric acid cycle-generated intermediates in the regulation of cancer cell proliferation has been recently appreciated. One function of MCTs (monocarboxylate transporters) is to transport the citric acid cycle substrate pyruvate across the plasma membrane and into mitochondria, and inhibition of MCTs has been proposed as a therapeutic strategy to target metabolic pathways in cancer. In the present paper, we examined the effect of different metabolic substrates (glucose and pyruvate) on mitochondrial function and proliferation in breast cancer cells. We demonstrated that cancer cells proliferate more rapidly in the presence of exogenous pyruvate when compared with lactate. Pyruvate supplementation fuelled mitochondrial oxygen consumption and the reserve respiratory capacity, and this increase in mitochondrial function correlated with proliferative potential. In addition, inhibition of cellular pyruvate uptake using the MCT inhibitor α-cyano-4-hydroxycinnamic acid impaired mitochondrial respiration and decreased cell growth. These data demonstrate the importance of mitochondrial metabolism in proliferative responses and highlight a novel mechanism of action for MCT inhibitors through suppression of pyruvate-fuelled mitochondrial respiration.

  7. The proton-linked monocarboxylate transporter (MCT) family: structure, function and regulation.

    PubMed Central

    Halestrap, A P; Price, N T

    1999-01-01

    Monocarboxylates such as lactate and pyruvate play a central role in cellular metabolism and metabolic communication between tissues. Essential to these roles is their rapid transport across the plasma membrane, which is catalysed by a recently identified family of proton-linked monocarboxylate transporters (MCTs). Nine MCT-related sequences have so far been identified in mammals, each having a different tissue distribution, whereas six related proteins can be recognized in Caenorhabditis elegans and 4 in Saccharomyces cerevisiae. Direct demonstration of proton-linked lactate and pyruvate transport has been demonstrated for mammalian MCT1-MCT4, but only for MCT1 and MCT2 have detailed analyses of substrate and inhibitor kinetics been described following heterologous expression in Xenopus oocytes. MCT1 is ubiquitously expressed, but is especially prominent in heart and red muscle, where it is up-regulated in response to increased work, suggesting a special role in lactic acid oxidation. By contrast, MCT4 is most evident in white muscle and other cells with a high glycolytic rate, such as tumour cells and white blood cells, suggesting it is expressed where lactic acid efflux predominates. MCT2 has a ten-fold higher affinity for substrates than MCT1 and MCT4 and is found in cells where rapid uptake at low substrate concentrations may be required, including the proximal kidney tubules, neurons and sperm tails. MCT3 is uniquely expressed in the retinal pigment epithelium. The mechanisms involved in regulating the expression of different MCT isoforms remain to be established. However, there is evidence for alternative splicing of the 5'- and 3'-untranslated regions and the use of alternative promoters for some isoforms. In addition, MCT1 and MCT4 have been shown to interact specifically with OX-47 (CD147), a member of the immunoglobulin superfamily with a single transmembrane helix. This interaction appears to assist MCT expression at the cell surface. There is still

  8. An enhanced procedure for measuring organic acids and methyl esters in PM2.5

    NASA Astrophysics Data System (ADS)

    Liu, F.; Duan, F.; He, K.; Ma, Y.; Rahn, K. A.; Zhang, Q.

    2015-03-01

    We have developed an enhanced analytical procedure to measure organic acids and methyl esters in fine aerosol with much greater specificity and sensitivity than previously available. This capability is important because of these species and their low concentrations, even in highly polluted atmospheres like Beijing, China. The procedure first separates the acids and esters from the other organic compounds with anion-exchange solid- phase extraction (SPE), then, quantifies them by gas chromatography coupled with mass spectrometry. This allows us to accurately quantify the C4-C11 dicarboxylic and the C8-C30 monocarboxylic acids. Then the acids are separated from the esters on an aminopropyl SPE cartridge, whose weak retention isolates and enriches the acids from esters prevents the fatty acids and dimethyl phthalate from being overestimated. The resulting correlations between the aliphatic acids and fatty acid methyl esters (FAMEs) suggest that FAMEs had sources similar to those of the carboxylic acids, or were formed by esterifying carboxylic acids, or that aliphatic acids were formed by hydrolyzing FAMEs. In all, 17 aromatic acids were identified and quantified using this procedure coupled with gas chromatography-tandem mass spectrometry, including the five polycyclic aromatic hydrocarbon (PAH) acids 2-naphthoic, biphenyl-4-carboxylic, 9-oxo-9H-fluorene-1-carboxylic, biphenyl-4,4´-dicarboxylic, and phenanthrene-1-carboxylic acid, plus 1,8-naphthalic anhydride. Correlations between the PAH-acids and the dicarboxylic and aromatic acids indicated that the first three acids and 1,8-naphthalic anhydride were mainly secondary, the last two mainly primary.

  9. Thermodynamics of Boroxine Formation from the Aliphatic Boronic Acid Monomers R–B(OH)2 (R = H, H3C, H2N, HO, and F): A Computational Investigation

    PubMed Central

    Bhat, Krishna L.; Markham, George D.; Larkin, Joseph D.; Bock, Charles W.

    2011-01-01

    Boroxines are the 6-membered cyclotrimeric dehydration products of organoboronic acids: 3 R– B(OH)2 → R3B3O3 + 3 H2O, and in recent years have emerged as a useful class of organoboron molecules with applications in organic synthesis both as reagents and catalysts, as structural components in boronic acid derived pharmaceutical agents, as anion acceptors and electrolyte additives for battery materials [AL Korich and PM Iovine, Dalton Trans. 39 (2010) 1423–1431]. Second-order Møller-Plesset perturbation theory, in conjunction with the Dunning-Woon correlation-consistent cc-pVDZ, aug-cc-pVDZ, cc-pVTZ, and aug-cc-pVTZ basis sets, was used to investigate the structures and relative energies of the endo-exo, anti, and syn conformers of the aliphatic boronic acids R–B(OH)2 (R = H, H3C, H2N, HO, and F), as well as the thermodynamics of their boroxine formation; single-point calculations at the MP2/aug-cc-pVQZ, MP2/aug-cc-pV5Z, and CCSD(T)/aug-cc-pVTZ level using the MP2/aug-cc-pVTZ optimized geometries were also performed in selected cases. The endo-exo conformer was generally lowest in energy in vacuo, as well as in PCM and CPCM models of aqueous and carbon tetrachloride media. The values of ΔH2980 for boroxine formation via dehydration from the endo-exo conformers of these aliphatic boronic acids ranged from −2.9 for (H2N)3B3O3 to +12.2 kcal/mol for H3B3O3 at the MP2/aug-cc-pVTZ level in vacuo; for H3B3O3 the corresponding values in PCM:UFF implicit carbon tetrachloride and aqueous media were +11.2 and +9.8 kcal/mol, respectively. Based on our calculations, we recommend that ΔHf(298 K) for boroxine listed in the JANAF compilation needs to be revised from −290.0 kcal/mol to approximately −277.0 kcal/mol. PMID:21650154

  10. An enhanced procedure for measuring organic acids and methyl esters in PM2.5

    NASA Astrophysics Data System (ADS)

    Liu, F.; Duan, F. K.; He, K. B.; Ma, Y. L.; Rahn, K. A.; Zhang, Q.

    2015-11-01

    A solid-phase extraction (SPE) pretreatment procedure allowing organic acids to be separated from methyl esters in fine aerosol has been developed. The procedure first separates the organic acids from fatty acid methyl esters (FAMEs) and other nonacid organic compounds by aminopropyl-based SPE cartridge and then quantifies them by gas chromatography/mass spectrometry. The procedure prevents the fatty acids and dimethyl phthalate from being overestimated, and so allows us to accurately quantify the C4-C11 dicarboxylic acids (DCAs) and the C8-C30 monocarboxylic acids (MCAs). Results for the extraction of DCAs, MCAs, and AMAs in eluate and FAMEs in effluate by SAX and NH2 SPE cartridges exhibited that the NH2 SPE cartridge gave higher extraction efficiency than the SAX cartridge. The recoveries of analytes ranged from 67.5 to 111.3 %, and the RSD ranged from 0.7 to 10.9 %. The resulting correlations between the aliphatic acids and FAMEs suggest that the FAMEs had sources similar to those of the carboxylic acids, or were formed by esterifying carboxylic acids, or that aliphatic acids were formed by hydrolyzing FAMEs. Through extraction and cleanup using this procedure, 17 aromatic acids in eluate were identified and quantified by gas chromatography/tandem mass spectrometry, including five polycyclic aromatic hydrocarbon (PAH): acids 2-naphthoic, biphenyl-4-carboxylic, 9-oxo-9H-fluorene-1-carboxylic, biphenyl-4,4´-dicarboxylic, and phenanthrene-1-carboxylic acid, plus 1,8-naphthalic anhydride. Correlations between the PAH acids and the dicarboxylic and aromatic acids suggested that the first three acids and 1,8-naphthalic anhydride were secondary atmospheric photochemistry products and the last two mainly primary.

  11. Cloning and functional identification of slc5a12 as a sodium-coupled low-affinity transporter for monocarboxylates (SMCT2)

    PubMed Central

    2005-01-01

    We report in the present paper, on the isolation and functional characterization of slc5a12, the twelfth member of the SLC5 gene family, from mouse kidney. The slc5a12 cDNA codes for a protein of 619 amino acids. Heterologous expression of slc5a12 cDNA in mammalian cells induces Na+-dependent transport of lactate and nicotinate. Several other short-chain monocarboxylates compete with nicotinate for the cDNA-induced transport process. Expression of slc5a12 in Xenopus oocytes induces electrogenic and Na+-dependent transport of lactate, nicotinate, propionate and butyrate. The substrate specificity of slc5a12 is similar to that of slc5a8, an Na+-coupled transporter for monocarboxylates. However, the substrate affinities of slc5a12 were much lower than those of slc5a8. slc5a12 mRNA is expressed in kidney, small intestine and skeletal muscle. In situ hybridization with sagittal sections of mouse kidney showed predominant expression of slc5a12 in the outer cortex. This is in contrast with slc5a8, which is expressed in the cortex as well as in the medulla. The physiological function of slc5a12 in the kidney is likely to mediate the reabsorption of lactate. In the intestinal tract, slc5a12 is expressed in the proximal parts, whereas slc5a8 is expressed in the distal parts. The expression of slc5a12 in the proximal parts of the intestinal tract, where there is minimal bacterial colonization, suggests that the physiological function of slc5a12 is not to mediate the absorption of short-chain monocarboxylates derived from bacterial fermentation but rather to mediate the absorption of diet-derived short-chain monocarboxylates. Based on the functional and structural similarities between slc5a8 and slc5a12, we suggest that the two transporters be designated as SMCT1 (sodium-coupled monocarboxylate transporter 1) and SMCT2 respectively. PMID:16104846

  12. Cloud condensation nuclei (CCN) activity of aliphatic amine secondary aerosol

    NASA Astrophysics Data System (ADS)

    Tang, X.; Price, D.; Praske, E.; Vu, D. N.; Purvis-Roberts, K.; Silva, P. J.; Cocker, D. R., III; Asa-Awuku, A.

    2014-06-01

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g., hydroxyl radical and nitrate radical). The particle can contain both secondary organic aerosol (SOA) and inorganic salts. The ratio of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, κ, ≤ 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N2O5 (source of nitrate radical, NO3) contains less volatile compounds than the primary aliphatic amine (BA) aerosol. As relative humidity (RH) increases, inorganic amine salts are formed as a result of acid-base reactions. The CCN activity of the humid TMA-N2O5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. The humid BA + N2O5 aerosol products were found to be very sensitive to the temperature at which the measurements were made within the streamwise continuous-flow thermal gradient CCN counter; κ ranges from 0.4 to 0.7 dependent on the instrument supersaturation (ss) settings. The variance of the measured aerosol κ values indicates that simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems' κ ranges within 0.2 < κ < 0.7. This work indicates that aerosols formed via nighttime reactions with amines are likely to produce hygroscopic and volatile aerosol, whereas photochemical reactions with OH produce secondary organic aerosol of lower CCN activity. The contributions of semivolatile secondary organic and inorganic material from aliphatic amines must be considered for accurate hygroscopicity and CCN predictions from aliphatic amine systems.

  13. A novel syndrome combining thyroid and neurological abnormalities is associated with mutations in a monocarboxylate transporter gene.

    PubMed

    Dumitrescu, Alexandra M; Liao, Xiao-Hui; Best, Thomas B; Brockmann, Knut; Refetoff, Samuel

    2004-01-01

    Thyroid hormones are iodothyronines that control growth and development, as well as brain function and metabolism. Although thyroid hormone deficiency can be caused by defects of hormone synthesis and action, it has not been linked to a defect in cellular hormone transport. In fact, the physiological role of the several classes of membrane transporters remains unknown. We now report, for the first time, mutations in the monocarboxylate transporter 8 (MCT8) gene, located on the X chromosome, that encodes a 613-amino acid protein with 12 predicted transmembrane domains. The propositi of two unrelated families are males with abnormal relative concentrations of three circulating iodothyronines, as well as neurological abnormalities, including global developmental delay, central hypotonia, spastic quadriplegia, dystonic movements, rotary nystagmus, and impaired gaze and hearing. Heterozygous females had a milder thyroid phenotype and no neurological defects. These findings establish the physiological importance of MCT8 as a thyroid hormone transporter. PMID:14661163

  14. 40 CFR 721.3364 - Aliphatic ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aliphatic ether. 721.3364 Section 721... Aliphatic ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an aliphatic ether (PMN P-93-1381) is subject to reporting under...

  15. 40 CFR 721.3364 - Aliphatic ether.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic ether. 721.3364 Section 721... Aliphatic ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an aliphatic ether (PMN P-93-1381) is subject to reporting under...

  16. [Role of Monocarboxylate Transporter in Statin-induced Cytotoxicity].

    PubMed

    Kobayashi, Masaki

    2015-01-01

    Although exercise and drug therapy are important to prevent progression of arteriosclerotic disease, exercise leads to an increase in muscular disorder induced by HMG-CoA reductase inhibitors (statins). Elucidation of this mechanism is needed to prevent the occurrence of muscular disorders. Since exercise induces expression of monocarboxylate transporter (MCT) 4, we focused on the association between MCT4 function and statin-induced muscle injury. First, we examined the transport of L-lactate via MCT4 using MCT4 cRNA-injected Xenopus laevis oocytes. L-lactate uptake by MCT4-expressing oocytes was markedly reduced by alkalizing the buffer pH and saturated at higher L-lactate concentrations. On the other hand, AMP-activated protein kinase (AMPK) and protein kinase C (PKC) are activated by exercise. We next examined whether AMPK and PKC activation affects the expression and function of MCT4 in rat skeletal muscle and RD cells as an in vitro skeletal muscle model. AMPK and PKC activation increased MCT4 expression level and lactate efflux by MCT4. Finally, we examined the association between MCT4 function and statin-induced cytotoxicity. Statins inhibited transport of L-lactate via MCT4 in a concentration-dependent manner. Statin-induced cytotoxicity was associated with intracellular acidification and caspase-3/7 activation. On the other hand, bicarbonate suppressed statin-induced pH alteration, caspase activation, and morphological change. The results suggest that statin-induced muscle injury exacerbated by exercise is associated with intracellular acidification and that the effects of statins on L-lactate transport are mediated by MCT4.

  17. Aliphatic hydrocarbons of the Murchison meteorite

    SciTech Connect

    Cronin, J.R.; Pizzarello, S. )

    1990-10-01

    The indigenous organic compounds of carbonaceous chondrites have been difficult to characterize because of problems arising from terrestrial contamination. The fall of the Murchison meteorite (CM2) provided pristine samples which allowed the resolution of some prior ambiguities as, for example, in the case of the amino acids. However, the nature of the aliphatic hydrocarbons has remained unclear. Shortly after the Murchison fall, one laboratory found them to be mainly cycloalkanes; another found, in order of abundance, branched alkanes, olefins, and cycloalkanes; while a third reported predominantly n-alkanes followed by methyl alkanes and olefins. The authors have reinvestigated this question using benzene-methanol as the extraction solvent, silica-gel chromatography for fractionation of the extract, and GC-MS, and IR and NMR spectroscopic techniques for the analyses. When interior samples were obtained and the analyses carried out under conditions that minimized environmental contaminants, they have found the principal aliphatic components of the Murchison meteorite to be a structurally diverse suite of C{sub 15} to C{sub 30} branched alkyl-substituted mono-, di-, and tricyclic alkanes. Comparative analyses were carried out on the Murray (CM2), Allende (CV3), and New Concord (L6) chondrites that illustrate the nature of the contamination problem encountered with carbonaceous chondrites.

  18. Aliphatic hydrocarbons of the Murchison meteorite.

    PubMed

    Cronin, J R; Pizzarello, S

    1990-01-01

    The indigenous organic compounds of carbonaceous chondrites have been difficult to characterize because of problems arising from terrestrial contamination. The fall of the Murchison meteorite (CM2) provided pristine samples which allowed the resolution of some prior ambiguities as, for example, in the case of the amino acids. However, the nature of the aliphatic hydrocarbons has remained unclear. Shortly after the Murchison fall, one laboratory found them to be mainly cycloalkanes; another found, in order of abundance, branched alkanes, olefins, and cycloalkanes; while a third reported predominantly n-alkanes followed by methyl alkanes and olefins. We have reinvestigated this question using benzene-methanol as the extraction solvent, silica-gel chromatography for fractionation of the extract, and GC-MS, and IR and NMR spectroscopic techniques for the analyses. When interior samples were obtained and the analyses carried out under conditions that minimized environmental contaminants, we have found the principal aliphatic components of the Murchison meteorite to be a structurally diverse suite of C15 to C30 branched alkyl-substituted mono-, di-, and tricyclic alkanes. Comparative analyses were carried out on the Murray (CM2), Allende (CV3), and New Concord (L6) chondrites that illustrate the nature of the contamination problem encountered with carbonaceous chondrites.

  19. Guided desaturation of unactivated aliphatics

    NASA Astrophysics Data System (ADS)

    Voica, Ana-Florina; Mendoza, Abraham; Gutekunst, Will R.; Fraga, Jorge Otero; Baran, Phil S.

    2012-08-01

    The excision of hydrogen from an aliphatic carbon chain to produce an isolated olefin (desaturation) without overoxidation is one of the most impressive and powerful biosynthetic transformations for which there are no simple and mild laboratory substitutes. The versatility of olefins and the range of reactions they undergo are unsurpassed in functional group space. Thus, the conversion of a relatively inert aliphatic system into its unsaturated counterpart could open new possibilities in retrosynthesis. In this article, the invention of a directing group to achieve such a transformation under mild, operationally simple, metal-free conditions is outlined. This ‘portable desaturase’ (TzoCl) is a bench-stable, commercial entity (Aldrich, catalogue number L510092) that is facile to install on alcohol and amine functionalities to ultimately effect remote desaturation, while leaving behind a synthetically useful tosyl group.

  20. Guided Desaturation of Unactivated Aliphatics

    PubMed Central

    Voica, Ana-Florina; Mendoza, Abraham; Gutekunst, Will R.; Fraga, Jorge Otero; Baran, Phil S.

    2012-01-01

    The excision of hydrogen from an aliphatic carbon chain to produce an isolated olefin (desaturation) without over-oxidation is one of the most impressive and powerful biosynthetic transformations for which there are no simple and mild laboratory substitutes. The versatility of olefins and the range of reactions they undergo is unsurpassed in functional group space. Thus, the conversion of a relatively inert aliphatic system to its unsaturated counterpart can open new possibilities in retrosynthesis. In this article, the invention of a directing group to achieve such a transformation under mild, operationally simple, metal-free conditions is outlined. This “portable desaturase” (TzoCl) is a bench-stable, commercial entity (Aldrich, cat # L510092) that is facile to install on alcohol and amine functionalities to ultimately effect remote desaturation, while leaving behind a synthetically useful tosyl group. PMID:22824894

  1. Scope and limitations of aliphatic Friedel-Crafts alkylations. Lewis acid catalyzed addition reactions of alkyl chlorides to carbon-carbon double bonds

    SciTech Connect

    Mayr, H.; Striepe, W.

    1983-04-22

    Lewis acid catalyzed addition reactions of alkyl halides with unsaturated hydrocarbons have been studied. 1:1 addition products are formed if the addends dissociate faster than the corresponding products; otherwise, polymerization takes place. For reaction conditions under which these compounds exist mainly undissociated, solvolysis constants of model compounds can be used to predict the outcome of any such addition reactions if systems with considerable steric hindrance are excluded.

  2. Aliphatic hydrocarbons of the fungi.

    NASA Technical Reports Server (NTRS)

    Weete, J. D.

    1972-01-01

    Review of studies of aliphatic hydrocarbons which have been recently detected in the spores of phytopathogenic fungi, and are found to be structurally very similar to the alkanes of higher plants. It appears that the hydrocarbon components of the few mycelial and yeast forms reported resemble the distribution found in bacteria. The occurence and distribution of these compounds in the fungi is discussed. Suggested functional roles of fungal spore alkanes are presented.

  3. Time-resolved FT EPR and optical spectroscopy study on photooxidation of aliphatic alpha-amino acids in aqueous solutions; electron transfer from amino vs carboxylate functional group.

    PubMed

    Tarabek, Peter; Bonifacić, Marija; Beckert, Dieter

    2006-06-01

    Using time-resolved Fourier transform electron paramagnetic resonance, FT EPR, and optical spectroscopy, the photooxidation of glycine, alpha-alanine, alpha-aminoisobutyric acid, and model compounds beta-alanine, methylamine and sodium acetate, by excited triplets of anthraquinone-2,6-disulfonate dianion was studied in aqueous solutions in the pH range 5-13. Anthraquinone radical trianions showing strong emissive spin-polarization (CIDEP) were formed, indicating fast electron transfer from the quenchers to the spin-polarized quinone triplet as the primary reaction. None of the primary radicals formed upon one-electron oxidation of quenchers could be detected at the nanosecond time scale of FT EPR measurements because of their very fast transformation into secondary products. The latter were identified to be decarboxylated alpha-aminoalkyl radicals for alpha-amino acids anions and zwitterions, beta-aminoalkyl radicals for beta-alanine zwitterions, and methyl radicals for acetate anions; corresponding aminyl radicals were the first EPR detectable products from beta-alanine anions and methylamine. Thus, anthraquinone-2,6-disulfonate triplet can take an electron from both NH(2)- and -CO(2)(-) functional groups forming aminium ((+*)NH(2)-) and acyloxyl (-CO(2)(*)) radicals, respectively. Aminium radicals derived from beta-alanine anions and CH(3)-NH(2) stabilize by deprotonation into aminyl radicals, whereas these derived from alpha-amino acids anions are known to suffer ultrafast decarboxylation (tau approximately 10 ps). Analysis of the polarization patterns revealed that decarboxylation from acyloxyl radicals are considerably slower (ns < tau < 0.1 micros). Therefore, in the case of alpha-amino acids, the isoelectronic structures NH(2)-CR(2)-CO(2)(*) and (+*)NH(2)-CR(2)-CO(2)(-) probably do not constitute resonance mesomeric forms of one and the same species and the decarboxylation of aminium radicals is not preceded by the intramolecular carboxylate to amino group

  4. Resistance to Diet-Induced Obesity and Associated Metabolic Perturbations in Haploinsufficient Monocarboxylate Transporter 1 Mice

    PubMed Central

    Steiner, Nadia; Carneiro, Lionel; Favrod, Céline; Preitner, Frédéric; Thorens, Bernard; Stehle, Jean-Christophe; Dix, Laure; Pralong, François; Magistretti, Pierre J.; Pellerin, Luc

    2013-01-01

    The monocarboxylate transporter 1 (MCT1 or SLC16A1) is a carrier of short-chain fatty acids, ketone bodies, and lactate in several tissues. Genetically modified C57BL/6J mice were produced by targeted disruption of the mct1 gene in order to understand the role of this transporter in energy homeostasis. Null mutation was embryonically lethal, but MCT1+/− mice developed normally. However, when fed high fat diet (HFD), MCT1+/− mice displayed resistance to development of diet-induced obesity (24.8% lower body weight after 16 weeks of HFD), as well as less insulin resistance and no hepatic steatosis as compared to littermate MCT1+/+ mice used as controls. Body composition analysis revealed that reduced weight gain in MCT1+/− mice was due to decreased fat accumulation (50.0% less after 9 months of HFD) notably in liver and white adipose tissue. This phenotype was associated with reduced food intake under HFD (12.3% less over 10 weeks) and decreased intestinal energy absorption (9.6% higher stool energy content). Indirect calorimetry measurements showed ∼ 15% increase in O2 consumption and CO2 production during the resting phase, without any changes in physical activity. Determination of plasma concentrations for various metabolites and hormones did not reveal significant changes in lactate and ketone bodies levels between the two genotypes, but both insulin and leptin levels, which were elevated in MCT1+/+ mice when fed HFD, were reduced in MCT1+/− mice under HFD. Interestingly, the enhancement in expression of several genes involved in lipid metabolism in the liver of MCT1+/+ mice under high fat diet was prevented in the liver of MCT1+/− mice under the same diet, thus likely contributing to the observed phenotype. These findings uncover the critical role of MCT1 in the regulation of energy balance when animals are exposed to an obesogenic diet. PMID:24367518

  5. Development of aliphatic biodegradable photoluminescent polymers

    PubMed Central

    Yang, Jian; Zhang, Yi; Gautam, Santosh; Liu, Li; Dey, Jagannath; Chen, Wei; Mason, Ralph P.; Serrano, Carlos A.; Schug, Kevin A.; Tang, Liping

    2009-01-01

    None of the current biodegradable polymers can function as both implant materials and fluorescent imaging probes. The objective of this study was to develop aliphatic biodegradable photoluminescent polymers (BPLPs) and their associated cross-linked variants (CBPLPs) for biomedical applications. BPLPs are degradable oligomers synthesized from biocompatible monomers including citric acid, aliphatic diols, and various amino acids via a convenient and cost-effective polycondensation reaction. BPLPs can be further cross-linked into elastomeric cross-linked polymers, CBPLPs. We have shown representatively that BPLP-cysteine (BPLP-Cys) and BPLP-serine (BPLP-Ser) offer advantages over the traditional fluorescent organic dyes and quantum dots because of their preliminarily demonstrated cytocompatibility in vitro, minimal chronic inflammatory responses in vivo, controlled degradability and high quantum yields (up to 62.33%), tunable fluorescence emission (up to 725 nm), and photostability. The tensile strength of CBPLP-Cys film ranged from 3.25 ± 0.13 MPa to 6.5 ± 0.8 MPa and the initial Modulus was in a range of 3.34 ± 0.15 MPa to 7.02 ± 1.40 MPa. Elastic CBPLP-Cys could be elongated up to 240 ± 36%. The compressive modulus of BPLP-Cys (0.6) (1:1:0.6 OD:CA:Cys) porous scaffold was 39.60 ± 5.90 KPa confirming the soft nature of the scaffolds. BPLPs also possess great processability for micro/nano-fabrication. We demonstrate the feasibility of using BPLP-Ser nanoparticles (“biodegradable quantum dots”) for in vitro cellular labeling and noninvasive in vivo imaging of tissue engineering scaffolds. The development of BPLPs and CBPLPs represents a new direction in developing fluorescent biomaterials and could impact tissue engineering, drug delivery, bioimaging. PMID:19506254

  6. Aerobic growth of campylobacter in media supplemented with C3-monocarboxylates and C4-dicarboxylates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Experiments were conducted to examine aerobic growth of Campylobacter spp. in media supplemented with C4-dicarboxylates (fumarate, succinate, or malate) and C3-monocarboxylates (pyruvate or lactate). Basal broth media composed of tryptose, yeast extract, and a mineral-vitamin solution was supplement...

  7. Redistribution of monocarboxylate transporter 2 on the surface of astrocytes in the human epileptogenic hippocampus

    PubMed Central

    Lauritzen, Fredrik; Heuser, Kjell; de Lanerolle, Nihal C.; Lee, Tih-Shih W.; Spencer, Dennis D.; Kim, Jung H.; Gjedde, Albert; Eid, Tore; Bergersena, Linda H.

    2013-01-01

    Emerging evidence points to monocarboxylates as key players in the pathophysiology of temporal lobe epilepsy (TLE) with hippocampal sclerosis (mesial temporal lobe epilepsy, MTLE). Monocarboxylate transporters (MCT) 1 and 2, which are abundantly present on brain endothelial cells and perivascular astrocyte endfeet, respectively, facilitate the transport of monocarboxylates and protons across cell membranes. Recently, we reported that the density of MCT1 protein is reduced on endothelial cells and increased on astrocyte plasma membranes in the hippocampal formation in patients with MTLE and in several animal models of the disorder. Because the perivascular astrocyte endfeet comprise an important part of the neurovascular unit we now assessed the distribution of the MCT2 in hippocampal formations in TLE patients with (MTLE) or without hippocampal sclerosis (non-MTLE). Light microscopic immunohistochemistry revealed significantly less perivascular MCT2 immunoreactivity in the hippocampal formation in MTLE (n=6) than in non-MTLE (n=6) patients, and to a lesser degree in non-MTLE than in non-epilepsy patients (n=4). Immunogold electron microscopy indicated that the loss of MCT2 protein occurred on perivascular astrocyte endfeet. Interestingly, the loss of MCT2 on astrocyte endfeet in MTLE (n=3) was accompanied by an upregulation of the protein on astrocyte membranes facing synapses in the neuropil, when compared with non-MTLE (n=3). We propose that the altered distribution of MCT1 and MCT2 in TLE (especially MTLE) limits the flux of monocarboxylates across the blood brain barrier and enhances the exchange of monocarboxylates within the brain parenchyma. PMID:22535546

  8. Bacterial isolates degrading aliphatic polycarbonates.

    PubMed

    Suyama, T; Hosoya, H; Tokiwa, Y

    1998-04-15

    Bacteria that degrade an aliphatic polycarbonate, poly(hexamethylene carbonate), were isolated from river water in Ibaraki. Prefecture, Japan, after enrichment in liquid medium containing poly(hexamethylene carbonate) suspensions as carbon source, and dilution to single cells. Four of the strains, 35L, WFF52, 61A and 61B2, degraded poly(hexamethylene carbonate) on agar plate containing suspended poly(hexamethylene carbonate). Degradation of poly(hexamethylene carbonate) was confirmed by gel permeation chromatography. Besides poly(hexamethylene carbonate), the strains were found to degrade poly(tetramethylene carbonate). The strains were characterized morphologically, physiologically, and by 16S rDNA sequence analysis. Strains 35L and WFF52 were tentatively identified as Pseudomonas sp. and Variovorax sp., respectively, while strains 61A and 61B2 constitute an unidentified branch within the beta subclass of the Proteobacteria.

  9. O2-Filled Swimbladder Employs Monocarboxylate Transporters for the Generation of O2 by Lactate-Induced Root Effect Hemoglobin

    PubMed Central

    Umezawa, Takahiro; Kato, Akira; Ogoshi, Maho; Ookata, Kayoko; Munakata, Keijiro; Yamamoto, Yoko; Islam, Zinia; Doi, Hiroyuki; Romero, Michael F.; Hirose, Shigehisa

    2012-01-01

    The swimbladder volume is regulated by O2 transfer between the luminal space and the blood In the swimbladder, lactic acid generation by anaerobic glycolysis in the gas gland epithelial cells and its recycling through the rete mirabile bundles of countercurrent capillaries are essential for local blood acidification and oxygen liberation from hemoglobin by the “Root effect.” While O2 generation is critical for fish flotation, the molecular mechanism of the secretion and recycling of lactic acid in this critical process is not clear. To clarify molecules that are involved in the blood acidification and visualize the route of lactic acid movement, we analyzed the expression of 17 members of the H+/monocarboxylate transporter (MCT) family in the fugu genome and found that only MCT1b and MCT4b are highly expressed in the fugu swimbladder. Electrophysiological analyses demonstrated that MCT1b is a high-affinity lactate transporter whereas MCT4b is a low-affinity/high-conductance lactate transporter. Immunohistochemistry demonstrated that (i) MCT4b expresses in gas gland cells together with the glycolytic enzyme GAPDH at high level and mediate lactic acid secretion by gas gland cells, and (ii) MCT1b expresses in arterial, but not venous, capillary endothelial cells in rete mirabile and mediates recycling of lactic acid in the rete mirabile by solute-specific transcellular transport. These results clarified the mechanism of the blood acidification in the swimbladder by spatially organized two lactic acid transporters MCT4b and MCT1b. PMID:22496829

  10. A Bio-Catalytic Approach to Aliphatic Ketones

    PubMed Central

    Xiong, Mingyong; Deng, Jin; Woodruff, Adam P.; Zhu, Minshan; Zhou, Jun; Park, Sun Wook; Li, Hui; Fu, Yao; Zhang, Kechun

    2012-01-01

    Depleting oil reserves and growing environmental concerns have necessitated the development of sustainable processes to fuels and chemicals. Here we have developed a general metabolic platform in E. coli to biosynthesize carboxylic acids. By engineering selectivity of 2-ketoacid decarboxylases and screening for promiscuous aldehyde dehydrogenases, synthetic pathways were constructed to produce both C5 and C6 acids. In particular, the production of isovaleric acid reached 32 g/L (0.22 g/g glucose yield), which is 58% of the theoretical yield. Furthermore, we have developed solid base catalysts to efficiently ketonize the bio-derived carboxylic acids such as isovaleric acid and isocaproic acid into high volume industrial ketones: methyl isobutyl ketone (MIBK, yield 84%), diisobutyl ketone (DIBK, yield 66%) and methyl isoamyl ketone (MIAK, yield 81%). This hybrid “Bio-Catalytic conversion” approach provides a general strategy to manufacture aliphatic ketones, and represents an alternate route to expanding the repertoire of renewable chemicals. PMID:22416247

  11. Method for continuous production of aromatic carboxylic acid

    SciTech Connect

    Abrams, K.J.

    1988-12-20

    This patent describes a method for the continuous production of an aromatic carboxylic acid product in a pressurized oxidation reactor by liquid-phase, exothermic oxidation of an aromatic alkyl feed with an oxygen-containing gas, in the presence of an aromatic alkyl feed with an oxygen-containing gas, in the presence of an oxidation catalyst and in an aqueous monocarboxylic C/sub 2/ to C/sub 6/ aliphatic acid solvent medium, wherein the heat generated during the course of the oxidation is removed from the reactor by vaporization of a portion of the reaction medium and water, wherein the resulting vapors are condensed in part in a reflux loop externally of the oxidation reactor to produce a condensate and a gaseous phase, and wherein at least a portion of the condensate is returned to the oxidation reactor, the improvement comprising a method for controlling within desired limits the concentration of water in the oxidation reactor, which comprises: partitioning the vapors into a parallel condensate having a relatively lesser water-to-solvent weight ratio and a vapor phase having a relatively greater water-to-solvent weight ratio; returning the partial condensate directly to the oxidation reactor as a direct reflux stream; withdrawing the vapor phase from the reflux loop as a vapor stream; subjecting the withdrawn vapor stream to heat exchange while decreasing the vapor stream pressure to less than the oxidation reactor pressure to thereby produce an aqueous aliphatic acid stream having a water-to-solvent weight ratio greater than that of the direct reflux stream.

  12. Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Epstein, S.; Krishnamurthy, R. V.; Cronin, J. R.; Pizzarello, S.; Yuen, G. U.

    1987-01-01

    The isotopic composition of hydrogen, nitrogen, and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite has been determined. The unusually high D/H and N-15/N-14 ratios in the amino acid fraction are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound and provide the first evidence suggesting a direct relationship between the massive organosynthesis occurring in interstellar clouds and the presence of prebiotic compounds in primitive planetary bodies.

  13. The anti-tumour agent lonidamine is a potent inhibitor of the mitochondrial pyruvate carrier and plasma membrane monocarboxylate transporters.

    PubMed

    Nancolas, Bethany; Guo, Lili; Zhou, Rong; Nath, Kavindra; Nelson, David S; Leeper, Dennis B; Blair, Ian A; Glickson, Jerry D; Halestrap, Andrew P

    2016-04-01

    Lonidamine (LND) is an anti-tumour drug particularly effective at selectively sensitizing tumours to chemotherapy, hyperthermia and radiotherapy, although its precise mode of action remains unclear. It has been reported to perturb the bioenergetics of cells by inhibiting glycolysis and mitochondrial respiration, whereas indirect evidence suggests it may also inhibit L-lactic acid efflux from cells mediated by members of the proton-linked monocarboxylate transporter (MCT) family and also pyruvate uptake into the mitochondria by the mitochondrial pyruvate carrier (MPC). In the present study, we test these possibilities directly. We demonstrate that LND potently inhibits MPC activity in isolated rat liver mitochondria (Ki2.5 μM) and co-operatively inhibits L-lactate transport by MCT1, MCT2 and MCT4 expressed in Xenopus laevisoocytes with K0.5 and Hill coefficient values of 36-40 μM and 1.65-1.85 respectively. In rat heart mitochondria LND inhibited the MPC with similar potency and uncoupled oxidation of pyruvate was inhibited more effectively (IC50~ 7 μM) than other substrates including glutamate (IC50~ 20 μM). In isolated DB-1 melanoma cells 1-10 μM LND increased L-lactate output, consistent with MPC inhibition, but higher concentrations (150 μM) decreased L-lactate output whereas increasing intracellular [L-lactate] > 5-fold, consistent with MCT inhibition. We conclude that MPC inhibition is the most sensitive anti-tumour target for LND, with additional inhibitory effects on MCT-mediated L-lactic acid efflux and glutamine/glutamate oxidation. Together these actions can account for published data on the selective tumour effects of LND onL-lactate, intracellular pH (pHi) and ATP levels that can be partially mimicked by the established MPC and MCT inhibitor α-cyano-4-hydroxycinnamate (CHC). PMID:26831515

  14. The anti-tumour agent lonidamine is a potent inhibitor of the mitochondrial pyruvate carrier and plasma membrane monocarboxylate transporters

    PubMed Central

    Nancolas, Bethany; Guo, Lili; Zhou, Rong; Nath, Kavindra; Nelson, David S.; Leeper, Dennis B.; Blair, Ian A.; Glickson, Jerry D.; Halestrap, Andrew P.

    2016-01-01

    Lonidamine (LND) is an anti-tumour drug particularly effective at selectively sensitising tumours to chemotherapy, hyperthermia and radiotherapy, although its precise mode of action remains unclear. It has been reported to perturb the bioenergetics of cells by inhibiting glycolysis and mitochondrial respiration, while indirect evidence suggests it may also inhibit L-lactic acid efflux from cells mediated by members of the proton-linked monocarboxylate transporter (MCT) family and also pyruvate uptake into the mitochondria by the mitochondrial pyruvate carrier (MPC). Here we test these possibilities directly. We demonstrate that LND potently inhibits MPC activity in isolated rat liver mitochondria (Ki 2.5 μM) and cooperatively inhibits L-lactate transport by MCT1, MCT2 and MCT4 expressed in Xenopus laevis oocytes with K0.5 and Hill Coefficient values of 36–40 μM and 1.65–1.85. In rat heart mitochondria LND inhibited the MPC with similar potency and uncoupled oxidation of pyruvate was inhibited more effectively (IC50 ~7 μM) than other substrates including glutamate (IC50 ~20 μM). In isolated DB-1 melanoma cells 1–10 μM LND increased L-lactate output, consistent with MPC inhibition, but higher concentrations (150 μM) decreased L-lactate output while increasing intracellular [L-lactate] > five-fold, consistent with MCT inhibition. We conclude that MPC inhibition is the most sensitive anti-tumour target for LND, with additional inhibitory effects on MCT-mediated L-lactic acid efflux and glutamine/glutamate oxidation. Together these actions can account for published data on the selective tumour effects of LND on L-lactate, intracellular pH (pHi) and ATP levels that can be partially mimicked by the established MPC and MCT inhibitor α-cyano-4-hydroxycinnamate. PMID:26831515

  15. Monocarboxylate transporter 1 contributes to growth factor-induced tumor cell migration independent of transporter activity

    PubMed Central

    Gray, Alana L.; Coleman, David T.; Shi, Runhua; Cardelli, James A.

    2016-01-01

    Tumor progression to metastatic disease contributes to the vast majority of incurable cancer. Understanding the processes leading to advanced stage cancer is important for the development of future therapeutic strategies. Here, we establish a connection between tumor cell migration, a prerequisite to metastasis, and monocarboxylate transporter 1 (MCT1). MCT1 transporter activity is known to regulate aspects of tumor progression and, as such, is a clinically relevant target for treating cancer. Knockdown of MCT1 expression caused decreased hepatocyte growth factor (HGF)-induced as well as epidermal growth factor (EGF)-induced tumor cell scattering and wound healing. Western blot analysis suggested that MCT1 knockdown (KD) hinders signaling through the HGF receptor (c-Met) but not the EGF receptor. Exogenous, membrane-permeable MCT1 substrates were not able to rescue motility in MCT1 KD cells, nor was pharmacologic inhibition of MCT1 able to recapitulate decreased cell motility as seen with MCT1 KD cells, indicating transporter activity of MCT1 was dispensable for EGF- and HGF-induced motility. These results indicate MCT1 expression, independent of transporter activity, is required for growth factor-induced tumor cell motility. The findings presented herein suggest a novel function for MCT1 in tumor progression independent of its role as a monocarboxylate transporter. PMID:27127175

  16. Efficient Activation of Pathogenic ΔPhe501 Mutation in Monocarboxylate Transporter 8 by Chemical and Pharmacological Chaperones.

    PubMed

    Braun, Doreen; Schweizer, Ulrich

    2015-12-01

    Monocarboxylate transporter 8 (MCT8) is a thyroid hormone transmembrane transporter expressed in many cell types, including neurons. Mutations that inactivate transport activity of MCT8 cause severe X-linked psychomotor retardation in male patients, a syndrome originally described as the Allan-Herndon-Dudley syndrome. Treatment options currently explored the focus on finding thyroid hormone-like compounds that bypass MCT8 and enter cells through different transporters. Because MCT8 is a multipass transmembrane protein, some pathogenic mutations affect membrane trafficking while potentially retaining some transporter activity. We explore here the effects of chemical and pharmacological chaperones on the expression and transport activity of the MCT8 mutant ΔPhe501. Dimethylsulfoxide, 4-phenylbutyric acid as well as its sodium salt, and the isoflavone genistein increase T3 uptake into MDCK1 cells stably transfected with mutant MCT8-ΔPhe501. We show that ΔPhe501 represents a temperature-sensitive mutant protein that is stabilized by the proteasome inhibitor MG132. 4-Phenylbutyrate has been used to stabilize ΔPhe508 mutant cystic fibrosis transmembrane conductance regulator protein and is in clinical use in patients with urea cycle defects. Genistein is enriched in soy and available as a nutritional supplement. It is effective in stabilizing MCT8-ΔPhe501 at 100 nM concentration. Expression of the L471P mutant is increased in response to phenylbutyrate, but T3 uptake activity is not induced, supporting the notion that the chaperone specifically increases membrane expression. Our findings suggest that certain pathogenic MCT8 mutants may be responsive to (co-)treatment with readily available compounds, which increase endogenous protein function. PMID:26368820

  17. Elevated Serum Triiodothyronine and Intellectual and Motor Disability with Paroxysmal Dyskinesia Caused by a Monocarboxylate Transporter 8 Gene Mutation

    ERIC Educational Resources Information Center

    Fuchs, Oliver; Pfarr, Nicole; Pohlenz, Joachim; Schmidt, Heinrich

    2009-01-01

    "Monocarboxylate transporter 8" ("MCT8" or SLC16A2) is important for the neuronal uptake of triiodothyronine (T3) in its function as a specific and active transporter of thyroid hormones across the cell membrane, thus being essential for human brain development. We report on a German male with Allan-Herndon-Dudley syndrome presenting with severe…

  18. The first example of a zirconium-oxide based metal-organic framework constructed from monocarboxylate ligands.

    PubMed

    Liang, Weibin; Babarao, Ravichandar; Murphy, Michael J; D'Alessandro, Deanna M

    2015-01-28

    This work reports the first example of a Zr-based MOF which is exclusively constructed from the monocarboxylate ligand formate. Despite the low surface area, the new material exhibits an unexpectedly favourable affinity for carbon dioxide over nitrogen at room temperature.

  19. 40 CFR 721.10534 - Brominated aliphatic alcohol (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Brominated aliphatic alcohol (generic... Specific Chemical Substances § 721.10534 Brominated aliphatic alcohol (generic). (a) Chemical substance and... aliphatic alcohol (PMN P-12-260) is subject to reporting under this section for the significant new...

  20. 40 CFR 721.10534 - Brominated aliphatic alcohol (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Brominated aliphatic alcohol (generic... Specific Chemical Substances § 721.10534 Brominated aliphatic alcohol (generic). (a) Chemical substance and... aliphatic alcohol (PMN P-12-260) is subject to reporting under this section for the significant new...

  1. 40 CFR 721.3520 - Aliphatic polyglycidyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic polyglycidyl ether. 721.3520... Substances § 721.3520 Aliphatic polyglycidyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aliphatic polyglycidyl ether (PMN P-89-1036) is subject...

  2. 40 CFR 721.3520 - Aliphatic polyglycidyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aliphatic polyglycidyl ether. 721.3520... Substances § 721.3520 Aliphatic polyglycidyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance aliphatic polyglycidyl ether (PMN P-89-1036) is subject...

  3. Enzymatic degradation of aliphatic nitriles by Rhodococcus rhodochrous BX2, a versatile nitrile-degrading bacterium.

    PubMed

    Fang, Shumei; An, Xuejiao; Liu, Hongyuan; Cheng, Yi; Hou, Ning; Feng, Lu; Huang, Xinning; Li, Chunyan

    2015-06-01

    Nitriles are common environmental pollutants, and their removal has attracted increasing attention. Microbial degradation is considered to be the most acceptable method for removal. In this work, we investigated the biodegradation of three aliphatic nitriles (acetonitrile, acrylonitrile and crotononitrile) by Rhodococcus rhodochrous BX2 and the expression of their corresponding metabolic enzymes. This organism can utilize all three aliphatic nitriles as sole carbon and nitrogen sources, resulting in the complete degradation of these compounds. The degradation kinetics were described using a first-order model. The degradation efficiency was ranked according to t1/2 as follows: acetonitrile>trans-crotononitrile>acrylonitrile>cis-crotononitrile. Only ammonia accumulated following the three nitriles degradation, while amides and carboxylic acids were transient and disappeared by the end of the assay. mRNA expression and enzyme activity indicated that the tested aliphatic nitriles were degraded via both the inducible NHase/amidase and the constitutive nitrilase pathways, with the former most likely preferred.

  4. Aliphatic long-chain C20 polyesters from olefin metathesis.

    PubMed

    Trzaskowski, Justyna; Quinzler, Dorothee; Bährle, Christian; Mecking, Stefan

    2011-09-01

    Self-metathesis of undecenoic acid with [(PCy3)2Cl2Ru=CHPh] (2), followed by exhaustive hydrogenation yielded pure 1,20-eicosanedioic acid (5) (>99%) free of side-products from isomerization. Polycondensation with eicosane-1,20-diol (6), formed by reduction of the diol, yielded polyester 20,20 (Tm = 108 °C). By comparison, the known ADMET polymerization of undec-10-enyl undec-10-enoate (7), and subsequent exhaustive polymer-analogous hydrogenation yielded a polyester (poly-8) with irregular structure of the ester groups in the polymer chain (-O(C=O)- vs. -C(=O)O-) (Tm = 103 °C). Hydrogenation of secondary dispersions of poly-7 yielded aqueous dispersions of the long-chain aliphatic polyester poly-8.

  5. Renaissance of Aliphatic Polycarbonates: New Techniques and Biomedical Applications

    PubMed Central

    Xu, Jianwen; Feng, Ellva; Song, Jie

    2014-01-01

    Aliphatic polycarbonates were discovered a long time ago, with their conventional applications mostly limited to low molecular weight oligomeric intermediates for copolymerization with other polymers. Recent developments in polymerization techniques have overcome the difficulty in preparing high molecular weight aliphatic polycarbonates. These in turn, along with new functional monomers, have enabled the preparation of a wide range of aliphatic polycarbonates with diverse chemical compositions and structures. This review summarizes the latest polymerization techniques for preparing well-defined functional aliphatic polycarbonates, as well as the new applications of those aliphatic polycarbonates, esecially in the biomedical field. PMID:24994939

  6. Combinations of Aromatic and Aliphatic Radiolysis.

    PubMed

    LaVerne, Jay A; Dowling-Medley, Jennifer

    2015-10-01

    The production of H(2) in the radiolysis of benzene, methylbenzene (toluene), ethylbenzene, butylbenzene, and hexylbenzene with γ-rays, 2-10 MeV protons, 5-20 MeV helium ions, and 10-30 MeV carbon ions is used as a probe of the overall radiation sensitivity and to determine the relative contributions of aromatic and aliphatic entities in mixed hydrocarbons. The addition of an aliphatic side chain with progressively from one to six carbon lengths to benzene increases the H(2) yield with γ-rays, but the yield seems to reach a plateau far below that found from a simple aliphatic such as cyclohexane. There is a large increase in H(2) with LET (linear energy transfer) for all of the substituted benzenes, which indicates that the main process for H(2) formation is a second-order process and dominated by the aromatic entity. The addition of a small amount of benzene to cyclohexane can lower the H(2) yield from the value expected from a simple mixture law. A 50:50% volume mixture of benzene-cyclohexane has essentially the same H(2) yield as cyclohexylbenzene at a wide variation in LET, suggesting that intermolecular energy transfer is as efficient as intramolecular energy transfer.

  7. Spider monkeys (Ateles geoffroyi) are less sensitive to the odor of aliphatic ketones than to the odor of other classes of aliphatic compounds.

    PubMed

    Eliasson, Moa; Hernandez Salazar, Laura Teresa; Laska, Matthias

    2015-10-01

    Aliphatic ketones are widely present in body-borne and food odors of primates. Therefore, we used an operant conditioning paradigm and determined olfactory detection thresholds in four spider monkeys for a homologous series of aliphatic 2-ketones (2-butanone to 2-nonanone) and two of their isomers (3- and 4-heptanone). We found that, with the exception of the two shortest-chained ketones, all animals detected concentrations <1 ppm (parts per million), and with five odorants individual animals even reached threshold values <0.1 ppm. Further, we found a significant correlation between olfactory sensitivity of the spider monkeys and carbon chain length of the 2-ketones which can best be described as a U-shaped function. In contrast, no significant correlation was found between olfactory sensitivity and position of the functional carbonyl group. Across-odorant and across-species comparisons revealed the following: spider monkeys are significantly less sensitive to the odors of aliphatic ketones than to the odor of other classes of aliphatic compounds (1-alcohols, n-aldehydes, n-acetic esters, and n-carboxylic acids) sharing the same carbon length. Spider monkeys do not differ significantly in their olfactory sensitivity for aliphatic ketones from squirrel monkeys and pigtail macaques, but are significantly less sensitive to these odorants compared to human subjects and mice. These findings support the notion that neuroanatomical and genetic properties do not allow for reliable predictions with regard to a species' olfactory sensitivity. Further, we conclude that the frequency of occurrence of a class of odorants in a species' chemical environment does not allow for reliable predictions of the species' olfactory sensitivity. PMID:26055441

  8. Mass spectrometry study of the sublimation of aliphatic dipeptides

    NASA Astrophysics Data System (ADS)

    Badelin, V. G.; Tyunina, E. Yu.; Krasnov, A. V.; Tyunina, V. V.; Giricheva, N. I.; Girichev, A. V.

    2012-03-01

    The sublimation of glycyl-L-α-alanine (Gly-Ala), L-α-alanyl-L-α-alanine (Ala-Ala), and DL-α-alanyl-DL-α-valine (Ala-Val) aliphatic dipeptides is studied by electron ionization mass spectrometry in combination with Knudsen effusion. The temperature range in which substances sublime as monomer molecular forms is determined. Enthalpies of sublimation Δs H°( T) are determined for Gly-Ala, Ala-Ala, and Ala-Val. It is shown that the enthalpy of sublimation of dipeptides increases with an increase in the side hydrocarbon radical. The unknown Δs H°(298) values for 17 amino acids and nine dipeptides are estimated using the proposed "structure-property" correlation model, in which the geometry and electron characteristics of molecules are used as structural descriptors.

  9. CYP79F1 and CYP79F2 have distinct functions in the biosynthesis of aliphatic glucosinolates in Arabidopsis.

    PubMed

    Chen, Sixue; Glawischnig, Erich; Jørgensen, Kirsten; Naur, Peter; Jørgensen, Bodil; Olsen, Carl-Erik; Hansen, Carsten H; Rasmussen, Hasse; Pickett, John A; Halkier, Barbara A

    2003-03-01

    Cytochromes P450 of the CYP79 family catalyze the conversion of amino acids to oximes in the biosynthesis of glucosinolates, a group of natural plant products known to be involved in plant defense and as a source of flavor compounds, cancer-preventing agents and bioherbicides. We report a detailed biochemical analysis of the substrate specificity and kinetics of CYP79F1 and CYP79F2, two cytochromes P450 involved in the biosynthesis of aliphatic glucosinolates in Arabidopsis thaliana. Using recombinant CYP79F1 and CYP79F2 expressed in Escherichia coli and Saccharomyces cerevisiae, respectively, we show that CYP79F1 metabolizes mono- to hexahomomethionine, resulting in both short- and long-chain aliphatic glucosinolates. In contrast, CYP79F2 exclusively metabolizes long-chain elongated penta- and hexahomomethionines. CYP79F1 and CYP79F2 are spatially and developmentally regulated, with different gene expression patterns. CYP79F2 is highly expressed in hypocotyl and roots, whereas CYP79F1 is strongly expressed in cotyledons, rosette leaves, stems, and siliques. A transposon-tagged CYP79F1 knockout mutant completely lacks short-chain aliphatic glucosinolates, but has an increased level of long-chain aliphatic glucosinolates, especially in leaves and seeds. The level of long-chain aliphatic glucosinolates in a transposon-tagged CYP79F2 knockout mutant is substantially reduced, whereas the level of short-chain aliphatic glucosinolates is not affected. Biochemical characterization of CYP79F1 and CYP79F2, and gene expression analysis, combined with glucosinolate profiling of knockout mutants demonstrate the functional role of these enzymes. This provides valuable insights into the metabolic network leading to the biosynthesis of aliphatic glucosinolates, and into metabolic engineering of altered aliphatic glucosinolate profiles to improve nutritional value and pest resistance. PMID:12609033

  10. Novel synthetic method for the preparation of amphiphilic hyaluronan by means of aliphatic aromatic anhydrides.

    PubMed

    Huerta-Angeles, Gloria; Bobek, Martin; Příkopová, Eva; Šmejkalová, Daniela; Velebný, Vladimír

    2014-10-13

    The present work describes a novel and efficient method of synthesis of amphiphilic hyaluronan (HA) by esterification with alkyl fatty acids. These derivatives were synthesized under mild aqueous and well controlled conditions using mixed aliphatic aromatic anhydrides. These anhydrides characterized by the general formula RCOOCOC6H2Cl3 can be easily prepared by the reaction of the corresponding fatty acid (R) with 2,4,6-trichlorobenzoyl chloride (TCBC) in the presence of triethylamine. The aliphatic aromatic anhydrides RCOOCOC6H2Cl3 then react with the polysaccharide and enable the synthesis of aliphatic acid esters of HA in good yields. No hydrolytic degradation of hyaluronic acid could be observed. Parameters controlling the degree of esterification were systematically studied. Fatty acids with different chain lengths can be introduced applying this methodology. The degree of substitution was decreasing with increasing length of hydrophobic chain. The reaction products were fully characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), SEC-MALLS and chromatographic analyses. Although the esterified HA products exhibited aggregation in solution as demonstrated by NMR, microscopy and rheology, they were still water-soluble.

  11. Perinatal and early postnatal changes in the expression of monocarboxylate transporters MCT1 and MCT2 in the rat forebrain.

    PubMed

    Baud, Olivier; Fayol, Laurence; Gressens, Pierre; Pellerin, Luc; Magistretti, Pierre; Evrard, Philippe; Verney, Catherine

    2003-10-20

    In addition to glucose, monocarboxylates including lactate represent a major source of energy for the brain, especially during development. We studied the immunocytochemical expression of the monocarboxylate transporters MCT1 and MCT2 in the rat brain between embryonic day (E) 16 and postnatal day (P) 14. At E16-18, MCT1-like immunoreactivity was found throughout the cortical anlage, being particularly marked medially in the hippocampal anlage next to the ventricle. In a complementary pattern, MCT2-like immunoreactivity was expressed along the medial and ventral border of the ventricle in the medial septum and habenula before birth. The hypothalamic area exhibited MCT2 and MCT1 positive areas from E18 on. These transient labelings revealed four main sites of monocarboxylate and/or glucose exchange: the brain parenchyma, the epithelial cells, the ependymocytes, and the glia limitans. During the first postnatal week, MCT1 immunoreactivity extended massively to the vessel walls and moderately to the developing astrocytes in the cortex. In contrast, MCT2 immunoreactivity was faint in blood vessels but massive in developing astrocytes from P3 to P7. Neither MCT2 nor MCT1 colocalized with neuronal, microglial, or oligodendrocytic markers during the first postnatal week. At P14, a part of the scattered punctate MCT2 staining could be associated with astrocytes and postsynaptic dendritic labeling. The transient pattern of expression of MCTs throughout the perinatal period suggests a potential relationship with the maturation of the blood-brain barrier. PMID:12966567

  12. Spreading coefficients of aliphatic hydrocarbons on water

    SciTech Connect

    Takii, Taichi; Mori, Y.H. . Dept. of Mechanical Engineering)

    1993-11-01

    Experiments have been performed to determine the equilibrium spreading coefficients of some aliphatic hydrocarbons (C[sub 6]C[sub 10]) on water. The thickness of a discrete lens of each hydrocarbon sample floating on a stagnant water pool was measured interferometrically and used to calculate the spreading coefficient of the hydrocarbon with the aid of Langmuir's capillarity theory. The dependences of the spreading coefficient, thus observed, on temperature (0--50 C) and on the number of carbon atoms in the hydrocarbon molecule are in qualitative agreement with the predictions based on the Lifshitz theory of van der Waals forces.

  13. Amino and fatty acids in carbonaceous meteorites

    NASA Technical Reports Server (NTRS)

    Kvenvolden, K. A.

    1974-01-01

    Analyses of two carbonaceous meteorites have provided much of the latest evidence which seems to support Oparin's theory on the origin of life. The meteorites involved are the Murray meteorite, which fell in 1950, and the Murchison meteorite, which fell in 1969. The amino acids in the two meteorites are similar in composition. Eight of the twenty amino acids found belong to amino acids present in proteins. A number of monocarboxylic and dicarboxylic fatty acids were also found in the meteorites.

  14. Biofiltration of gasoline and diesel aliphatic hydrocarbons.

    PubMed

    Halecky, Martin; Rousova, Jana; Paca, Jan; Kozliak, Evguenii; Seames, Wayne; Jones, Kim

    2015-02-01

    The ability of a biofilm to switch between the mixtures of mostly aromatic and aliphatic hydrocarbons was investigated to assess biofiltration efficiency and potential substrate interactions. A switch from gasoline, which consisted of both aliphatic and aromatic hydrocarbons, to a mixture of volatile diesel n-alkanes resulted in a significant increase in biofiltration efficiency, despite the lack of readily biodegradable aromatic hydrocarbons in the diesel mixture. This improved biofilter performance was shown to be the result of the presence of larger size (C₉-C(12)) linear alkanes in diesel, which turned out to be more degradable than their shorter-chain (C₆-C₈) homologues in gasoline. The evidence obtained from both biofiltration-based and independent microbiological tests indicated that the rate was limited by biochemical reactions, with the inhibition of shorter chain alkane biodegradation by their larger size homologues as corroborated by a significant substrate specialization along the biofilter bed. These observations were explained by the lack of specific enzymes designed for the oxidation of short-chain alkanes as opposed to their longer carbon chain homologues.

  15. Gaseous aliphatic aldehydes in Chinese incense smoke

    SciTech Connect

    Lin, J.M.; Wang, L.H. )

    1994-09-01

    Aliphatic aldehydes were found during the combustion of materials. Tobacco smoke contains aldehydes. Fire fighters were exposed to aldehydes when they conducted firefighting. Aldehydes in ambient air come mainly from the incomplete combustion of hydrocarbons and from photochemical reaction. Most aldehydes in ambient air are formaldehyde and acetaldehyde. Formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and benzaldehyde were found in the atmosphere in Los Angeles. Burning Chinese incense for worshipping deities is a Chinese daily routine. It was suspected to be a factor causing nasopharynegeal cancer. Epidemiological studies correlated it with the high risk of childhood brain tumor and the high risk of childhood leukemia. Ames test identified the mutagenic effect of the smoke from burning Chinese incense. The smoke had bee proved to contain polycyclic aromatic hydrocarbons and aromatic aldehydes. Suspicion about formaldehyde and other alphatic aldehydes was evoked, when a survey of indoor air pollution was conducted in Taipei city. This study determined the presence of aliphatic aldehydes in the smoke from burning Chinese incense under a controlled atmosphere. 12 refs., 5 figs., 2 tabs.

  16. Biodegradation of aliphatic and aromatic polycarbonates.

    PubMed

    Artham, Trishul; Doble, Mukesh

    2008-01-01

    Polycarbonate is one of the most widely used engineering plastics because of its superior physical, chemical, and mechanical properties. Understanding the biodegradation of this polymer is of great importance to answer the increasing problems in waste management of this polymer. Aliphatic polycarbonates are known to biodegrade either through the action of pure enzymes or by bacterial whole cells. Very little information is available that deals with the biodegradation of aromatic polycarbonates. Biodegradation is governed by different factors that include polymer characteristics, type of organism, and nature of pretreatment. The polymer characteristics such as its mobility, tacticity, crystallinity, molecular weight, the type of functional groups and substituents present in its structure, and plasticizers or additives added to the polymer all play an important role in its degradation. The carbonate bond in aliphatic polycarbonates is facile and hence this polymer is easily biodegradable. On the other hand, bisphenol A polycarbonate contains benzene rings and quaternary carbon atoms which form bulky and stiff chains that enhance rigidity. Even though this polycarbonate is amorphous in nature because of considerable free volume, it is non-biodegradable since the carbonate bond is inaccessible to enzymes because of the presence of bulky phenyl groups on either side. In order to facilitate the biodegradation of polymers few pretreatment techniques which include photo-oxidation, gamma-irradiation, or use of chemicals have been tested. Addition of biosurfactants to improve the interaction between the polymer and the microorganisms, and blending with natural or synthetic polymers that degrade easily, can also enhance the biodegradation.

  17. Sodium hypochlorite oxidation of petroleum aliphatic contaminants in calcareous soils.

    PubMed

    Picard, François; Chaouki, Jamal

    2016-02-01

    This research project investigated the sodium hypochlorite (NaClO) oxidation of aliphatic petroleum contaminants (C10-C50) in a calcareous soil (average 5473 ppm C10-C50, 15 wt% Ca), which had been excavated from a contaminated industrial site. The decontamination objective was to lower the C10-C50 concentration to 700 ppm. CO2 acidity was used in the project to boost the NaClO oxidation yield and seems to have played a role in desorbing the natural organic matter. The experimental conditions were a 2- to 16-h reaction time, at room temperature, with a 1 to 12.5 wt% NaClO oxidative solution and a fixed 2:1 solution-to-soil ratio. With a 3 wt% NaClO solution and with a CO2 overhead, the NaClO dosage requirement was maintained below 60 g NaClO/g of oxidized C10-C50 over the entire decontamination range. The strong chlorine smell remaining after the reaction was completed suggests that part of the NaClO requirement can be recycled. Except traces of chloroform, there were no regulation-listed organochloride contaminants detected on either the treated soil samples or leachates and the total count of chlorinated compounds in treated soil samples was below the detection limit of 250 mg/kg. The NaClO oxidation mechanism on aliphatic substrates might be triggered by transition metals, such as manganese, but no attempt has been made to investigate the oxidation mechanism. Further investigations would include a constant-fed NaClO system and other techniques to lower the required NaClO dosage.

  18. Intracellular and Extracellular Carbonic Anhydrases Cooperate Non-enzymatically to Enhance Activity of Monocarboxylate Transporters*

    PubMed Central

    Klier, Michael; Andes, Fabian T.; Deitmer, Joachim W.; Becker, Holger M.

    2014-01-01

    Proton-coupled monocarboxylate transporters (MCTs) are carriers of high-energy metabolites such as lactate, pyruvate, and ketone bodies and are expressed in most tissues. It has previously been shown that transport activity of MCT1 and MCT4 is enhanced by the cytosolic carbonic anhydrase II (CAII) independent of its catalytic activity. We have now studied the influence of the extracellular, membrane-bound CAIV on transport activity of MCT1/4, heterologously expressed in Xenopus oocytes. Coexpression of CAIV with MCT1 and MCT4 resulted in a significant increase in MCT transport activity, even in the nominal absence of CO2/HCO3−. CAIV-mediated augmentation of MCT activity was independent of the CAIV catalytic function, since application of the CA-inhibitor ethoxyzolamide or coexpression of the catalytically inactive mutant CAIV-V165Y did not suppress CAIV-mediated augmentation of MCT transport activity. The interaction required CAIV at the extracellular surface, since injection of CAIV protein into the oocyte cytosol did not augment MCT transport function. The effects of cytosolic CAII (injected as protein) and extracellular CAIV (expressed) on MCT transport activity, were additive. Our results suggest that intra- and extracellular carbonic anhydrases can work in concert to ensure rapid shuttling of metabolites across the cell membrane. PMID:24338019

  19. Enhanced expression of three monocarboxylate transporter isoforms in the brain of obese mice

    PubMed Central

    Pierre, Karin; Parent, Annabelle; Jayet, Pierre-Yves; Halestrap, Andrew P; Scherrer, Urs; Pellerin, Luc

    2007-01-01

    Monocarboxylate transporters (MCTs) are membrane carriers for lactate and ketone bodies. Three isoforms, MCT1, MCT2 and MCT4, have been described in the central nervous system but little information is available about the regulation of their expression in relation to altered metabolic and/or nutritional conditions. We show here that brains of mice fed on a high fat diet (HFD) up to 12 weeks as well as brains of genetically obese (ob/ob) or diabetic (db/db) mice exhibit an increase of MCT1, MCT2 and MCT4 expression as compared to brains of control mice fed a standard diet. Enhanced expression of each transporter was visible throughout the brain but most prominently in the cortex and in the hippocampus. Using immunohistochemistry, we observed that neurons (expressing mainly MCT2 but also sometimes low levels of MCT1 under normal conditions) were immunolabelled for all three transporters in HFD mice as well as in ob/ob and db/db mice. At the subcellular level, changes were most remarkable in neuronal cell bodies. Western blotting performed on brain structure extracts allowed us to confirm quantitatively the enhancement of MCT1 and MCT2 expression. Our data demonstrate that the expression of cerebral MCT isoforms can be modulated by alterations of peripheral metabolism, suggesting that the adult brain is sensitive and adapts to new metabolic states. This observation could be relevant in the context of obesity development and its consequences for brain function. PMID:17599960

  20. Abnormal thyroid hormone metabolism in mice lacking the monocarboxylate transporter 8.

    PubMed

    Trajkovic, Marija; Visser, Theo J; Mittag, Jens; Horn, Sigrun; Lukas, Jan; Darras, Veerle M; Raivich, Genadij; Bauer, Karl; Heuer, Heike

    2007-03-01

    In humans, inactivating mutations in the gene of the thyroid hormone transporter monocarboxylate transporter 8 (MCT8; SLC16A2) lead to severe forms of psychomotor retardation combined with imbalanced thyroid hormone serum levels. The MCT8-null mice described here, however, developed without overt deficits but also exhibited distorted 3,5,3'-triiodothyronine (T3) and thyroxine (T4) serum levels, resulting in increased hepatic activity of type 1 deiodinase (D1). In the mutants' brains, entry of T4 was not affected, but uptake of T3 was diminished. Moreover, the T4 and T3 content in the brain of MCT8-null mice was decreased, the activity of D2 was increased, and D3 activity was decreased, indicating the hypothyroid state of this tissue. In the CNS, analysis of T3 target genes revealed that in the mutants, the neuronal T3 uptake was impaired in an area-specific manner, with strongly elevated thyrotropin-releasing hormone transcript levels in the hypothalamic paraventricular nucleus and slightly decreased RC3 mRNA expression in striatal neurons; however, cerebellar Purkinje cells appeared unaffected, since they did not exhibit dendritic outgrowth defects and responded normally to T3 treatment in vitro. In conclusion, the circulating thyroid hormone levels of MCT8-null mice closely resemble those of humans with MCT8 mutations, yet in the mice, CNS development is only partially affected. PMID:17318265

  1. Skeletal muscle monocarboxylate transporter content is not different between black and white runners.

    PubMed

    Harley, Yolande X R; Kohn, Tertius A; St Clair Gibson, Alan; Noakes, Timothy D; Collins, Malcolm

    2009-03-01

    The superior performance of black African runners has been associated with lower plasma lactate concentrations at sub-maximal intensities compared to white runners. The aim was to investigate the monocarboxylate transporters 1 (MCT1) and MCT4 content in skeletal muscle of black and white runners. Although black runners exhibited lower plasma lactate concentrations after maximum exercise (8.8 +/- 2.0 vs. 12.3 +/- 2.7 mmol l(-1), P < 0.05) and a tendency to be lower at 16 km h(-1) (2.4 +/- 0.7 vs. 3.8 +/- 2.4 mmol l(-1), P = 0.07) than the white runners, there were no differences in MCT1 or MCT4 levels between the two groups. For black and white runners together, MCT4 content correlated significantly with 10 km personal best time (r = -0.74, P < 0.01) and peak treadmill speed (r = 0.88, P < 0.001), but MCT1 content did not. Although whole homogenate MCT content was not different between the groups, more research is required to explain the lower plasma lactate concentrations in black runners.

  2. The Monocarboxylate Transporter 4 Is Required for Glycolytic Reprogramming and Inflammatory Response in Macrophages*

    PubMed Central

    Tan, Zheng; Xie, Na; Banerjee, Sami; Cui, Huachun; Fu, Mingui; Thannickal, Victor J.; Liu, Gang

    2015-01-01

    There has been fast growing evidence showing that glycolysis plays a critical role in the activation of immune cells. Enhanced glycolysis leads to increased formation of intracellular lactate that is exported to the extracellular environment by monocarboxylate transporter 4 (MCT4). Although the biological activities of extracellular lactate have been well studied, it is less understood how the lactate export is regulated or whether lactate export affects glycolysis during inflammatory activation. In this study, we found that MCT4 is up-regulated by TLR2 and TLR4, but not TLR3 agonists in a variety of macrophages. The increased expression of MCT4 was mediated by MYD88 in a NF-κB-dependent manner. Furthermore, we found that MCT4 is required for macrophage activation upon TLR2 and TLR4 stimulations, as evidenced by attenuated expression of proinflammatory mediators in macrophages with MCT4 knockdown. Mechanistically, we found that MCT4 knockdown leads to enhanced intracellular accumulation of lactate and decreased glycolysis in LPS-treated macrophages. We found that LPS-induced expression of key glycolytic enzymes hexokinase 2 and 6-phosphofructo-2-kinase/fructose-2,6-biphosphatase 3 is diminished in macrophages with MCT4 knockdown. Our data suggest that MCT4 up-regulation represents a positive feedback mechanism in macrophages to maintain a high glycolytic rate that is essential to a fully activated inflammatory response. PMID:25406319

  3. 40 CFR 721.4497 - Aliphatic polyisocyanates (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Aliphatic polyisocyanates (generic name). 721.4497 Section 721.4497 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.4497 Aliphatic polyisocyanates (generic name). (a) Chemical...

  4. Metalloradical-catalyzed aliphatic carbon-carbon activation of cyclooctane.

    PubMed

    Chan, Yun Wai; Chan, Kin Shing

    2010-05-26

    The aliphatic carbon-carbon activation of c-octane was achieved via the addition of Rh(ttp)H to give Rh(ttp)(n-octyl) in good yield under mild reaction conditions. The aliphatic carbon-carbon activation was Rh(II)(ttp)-catalyzed and was very sensitive to porphyrin sterics.

  5. Aryl isomerization during aliphatic CH bond activation

    SciTech Connect

    Chamberlain, L.R.; Rothwell, I.P.

    1983-03-23

    The transition-metal-stablized benzyne or o-phenylene (n/sup 2/-C/sub 6/H/sub 4/) ligand has been shown to be both an interesting and reactive group. The ligand is normally generated in mononuclear systems by ..beta..- (ortho-) hydrogen abstraction from an aryl group, and this synthetic approach has allowed a stable example to be isolated and structurally characterized. Here the conclusive identification of a benzyne intermediate during the isomerization of a tantalum-aryl compound is reported. The reaction is interesting in that the ortho hydrogen is transferred to the carbon atom of a cyclometalated chelate, the reverse (isomerization) step thus involving the activation of an aliphatic CH bond by the intermediate benzyne.

  6. Validation of Alternatives to Aliphatic Isocyanate Polyurethanes

    NASA Technical Reports Server (NTRS)

    Curran, Jerome

    2007-01-01

    The National Aeronautics and Space Administration (NASA) Headquarters chartered the Acquisition Pollution Prevention (AP2) Office to coordinate agency activities affecting pollution prevention issues identified during system and component acquisition and sustainment processes. The primary objective of this effort is to demonstrate and validate alternatives to aliphatic isocyanate polyurethane coatings. Successful completion of this project will result in one or more isocyanate-free coating systems qualified for use at Air Force Space Command (AFSPC) and NASA centers participating in this study. The objective of this project is to qualify the candidates under the specifications for the standard system. This project will compare coating performance of the proposed alternatives to existing coating systems or standards.

  7. Stable isotope investigations of chlorinated aliphatic hydrocarbons.

    SciTech Connect

    Abrajano, T.; Heraty, L. J.; Holt, B. D.; Huang, L.; Sturchio, N. C.

    1999-06-01

    Stable isotope ratio measurements for carbon (C) and chlorine (Cl) can be used to elucidate the processes affecting transformation and transportation of chlorinated aliphatic hydrocarbons (CAHs) in the environment. Methods recently developed in our laboratory for isotopic analysis of CAHs have been applied to laboratory measurements of the kinetic isotope effects associated with aerobic degradation of dichloromethane (DCM) and with both anaerobic and aerobic cometabolic degradation of trichlomethene (TCE) in batch and column microbial cultures. These experimental determinations of fractionation factors are crucial for understanding the behavior of CAHs in complex natural systems, where the extent of biotransformation can be masked by dispersion and volatilization. We have also performed laboratory investigations of kinetic isotope effects accompanying evaporation of CAHs, as well as field investigations of natural attenuation and in situ remediation of CAHs in a number of contaminated shallow aquifers at sites operated by the federal government and the private sector.

  8. In Vitro and In Vivo Evidence for Active Brain Uptake of the GHB Analog HOCPCA by the Monocarboxylate Transporter Subtype 1.

    PubMed

    Thiesen, Louise; Kehler, Jan; Clausen, Rasmus P; Frølund, Bente; Bundgaard, Christoffer; Wellendorph, Petrine

    2015-08-01

    γ-Hydroxybutyric acid (GHB) is a recreational drug, a clinically prescribed drug in narcolepsy and alcohol dependence, and an endogenous substance that binds to both high- and low-affinity sites in the brain. For studying the molecular mechanisms and the biologic role of the GHB high-affinity binding sites, ligands with high and specific affinity are essential. The conformationally restricted GHB analog HOCPCA (3-hydroxycyclopent-1-enecarboxylic acid) is one such compound. The objective of this study was to investigate the transport of HOCPCA across the blood-brain barrier in vitro and in vivo and to investigate the hypothesis that HOCPCA, like GHB, is a substrate for the monocarboxylate transporters (MCTs). For in vitro uptake studies, MCT1, -2, and -4 were recombinantly expressed in Xenopus laevis oocytes, and the previously reported radioligand [(3)H]HOCPCA was used as substrate. HOCPCA inhibited the uptake of the endogenous MCT substrate l-[(14)C]lactate, and [(3)H]HOCPCA was shown to act as substrate for MCT1 and 2 (Km values in the low- to mid-millimolar range). Introducing single-point amino acid mutations into positions essential for MCT function supported that HOCPCA binds to the endogenous substrate pocket of MCTs. MCT1-mediated brain entry of HOCPCA (10 mg/kg s.c.) was further confirmed in vivo in mice by coadministration of increasing doses of the MCT inhibitor AR-C141990 [(R)-5-(3-hydroxypyrrolidine-1-carbonyl)-1-isobutyl-3-methyl-6-(quinolin-4-ylmethyl)thieno[2,3-d]pyrimidine-2,4(1H,3H)-dione], which inhibited brain penetration of HOCPCA in a dose-dependent manner (ID50 = 4.6 mg/kg). Overall, our study provides evidence that MCT1 is an important brain entry site for HOCPCA and qualifies for future in vivo studies with HOCPCA.

  9. NO3 and OH initiated secondary aerosol formation from aliphatic amines - salt formation and effect of water vapor

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aliphatic amines enter the atmosphere from a variety of sources, and have been detected existing in gas and particle phases in the atmosphere. Similar to ammonia, amines can form inorganic salt through acid-base reactions. However, the atmospheric behavior of amines with atmospheric oxidants (e.g. n...

  10. The monocarboxylate transporter homolog Mch5p catalyzes riboflavin (vitamin B2) uptake in Saccharomyces cerevisiae.

    PubMed

    Reihl, Petra; Stolz, Jürgen

    2005-12-01

    Riboflavin is a water-soluble vitamin (vitamin B2) required for the production of the flavin cofactors FMN and FAD. Mammals are unable to synthesize riboflavin and need a dietary supply of the vitamin. Riboflavin transport proteins operating in the plasma membrane thus have an important role in the absorption of the vitamin. However, their sequences remained elusive, and not a single eukaryotic riboflavin transporter is known to date. Here we used a genetic approach to isolate MCH5, a Saccharomyces cerevisiae gene with homology to mammalian monocarboxylate transporters, and characterize the protein as a plasma membrane transporter for riboflavin. This conclusion is based on the suppression of riboflavin biosynthetic mutants (rib mutants) by overexpression of MCH5 and by synthetic growth defects caused by deletion of MCH5 in rib mutants. We also show that cellular processes in multiple compartments are affected by deletion of MCH5 and localize the protein to the plasma membrane. Transport experiments in S. cerevisiae and Schizosaccharomyces pombe cells demonstrate that Mch5p is a high affinity transporter (Km = 17 microM) with a pH optimum at pH 7.5. Riboflavin uptake is not inhibited by protonophores, does not require metabolic energy, and operates by a facilitated diffusion mechanism. The expression of MCH5 is regulated by the cellular riboflavin content. This indicates that S. cerevisiae has a mechanism to sense riboflavin and avert riboflavin deficiency by increasing the expression of the plasma membrane transporter MCH5. Moreover, the other members of the MCH gene family appear to have unrelated functions.

  11. Mutant IDH1 expression is associated with down-regulation of monocarboxylate transporters

    PubMed Central

    Viswanath, Pavithra; Najac, Chloe; Izquierdo, Jose L.; Pankov, Aleksandr; Hong, Chibo; Eriksson, Pia; Costello, Joseph F.; Pieper, Russell O.; Ronen, Sabrina M.

    2016-01-01

    Mutations in isocitrate dehydrogenase 1 (IDH1) are characteristic of low-grade gliomas. We recently showed that mutant IDH1 cells reprogram cellular metabolism by down-regulating pyruvate dehydrogenase (PDH) activity. Reduced pyruvate metabolism via PDH could lead to increased pyruvate conversion to lactate. The goal of this study was therefore to investigate the impact of the IDH1 mutation on the pyruvate-to-lactate flux. We used 13C magnetic resonance spectroscopy and compared the conversion of hyperpolarized [1-13C]-pyruvate to [1-13C]-lactate in immortalized normal human astrocytes expressing mutant or wild-type IDH1 (NHAIDHmut and NHAIDHwt). Our results indicate that hyperpolarized lactate production is reduced in NHAIDHmut cells compared to NHAIDHwt. This reduction was associated with lower expression of the monocarboxylate transporters MCT1 and MCT4 in NHAIDHmut cells. Furthermore, hyperpolarized lactate production was comparable in lysates of NHAIDHmut and NHAIDHwt cells, wherein MCTs do not impact hyperpolarized pyruvate delivery and lactate production. Collectively, our findings indicated that lower MCT expression was a key contributor to lower hyperpolarized lactate production in NHAIDHmut cells. The SLC16A3 (MCT4) promoter but not SLC16A1 (MCT1) promoter was hypermethylated in NHAIDHmut cells, pointing to possibly different mechanisms mediating reduced MCT expression. Finally analysis of low-grade glioma patient biopsy data from The Cancer Genome Atlas revealed that MCT1 and MCT4 expression was significantly reduced in mutant IDH1 tumors compared to wild-type. Taken together, our study shows that reduced MCT expression is part of the metabolic reprogramming of mutant IDH1 gliomas. This finding could impact treatment and has important implications for metabolic imaging of mutant IDH1 gliomas. PMID:27144334

  12. Inward flux of lactate⁻ through monocarboxylate transporters contributes to regulatory volume increase in mouse muscle fibres.

    PubMed

    Lindinger, Michael I; Leung, Matthew J; Hawke, Thomas J

    2013-01-01

    Mouse and rat skeletal muscles are capable of a regulatory volume increase (RVI) after they shrink (volume loss resultant from exposure to solutions of increased osmolarity) and that this RVI occurs mainly by a Na-K-Cl-Cotransporter (NKCC)-dependent mechanism. With high-intensity exercise, increased extracellular osmolarity is accompanied by large increases in extracellular [lactate⁻]. We hypothesized that large increases in [lactate⁻] and osmolarity augment the NKCC-dependent RVI response observed with a NaCl (or sucrose)-induced increase in osmolarity alone; a response that is dependent on lactate⁻ influx through monocarboxylate transporters (MCTs). Single mouse muscle fibres were isolated and visualized under light microscopy under varying osmolar conditions. When solution osmolarity was increased by adding NaLac by 30 or 60 mM, fibres lost significantly less volume and regained volume sooner compared to when NaCl was used. Phloretin (MCT1 inhibitor) accentuated the volume loss compared to both NaLac controls, supporting a role for MCT1 in the RVI response in the presence of elevated [lactate⁻]. Inhibition of MCT4 (with pCMBS) resulted in a volume loss, intermediate to that seen with phloretin and NaLac controls. Bumetanide (NKCC inhibitor), in combination with pCMBS, reduced the magnitude of volume loss, but volume recovery was complete. While combined phloretin-bumetanide also reduced the magnitude of the volume loss, it also largely abolished the cell volume recovery. In conclusion, RVI in skeletal muscle exposed to raised tonicity and [lactate⁻] is facilitated by inward flux of solute by NKCC- and MCT1-dependent mechanisms. This work demonstrates evidence of a RVI response in skeletal muscle that is facilitated by inward flux of solute by MCT-dependent mechanisms. These findings further expand our understanding of the capacities for skeletal muscle to volume regulate, particularly in instances of raised tonicity and lactate⁻ concentrations, as

  13. Monocarboxylate transporters in temporal lobe epilepsy: roles of lactate and ketogenic diet.

    PubMed

    Lauritzen, Fredrik; Eid, Tore; Bergersen, Linda H

    2015-01-01

    Epilepsy is a serious neurological disorder that affects approximately 1 % of the general population, making it one of the most common disorders of the central nervous system. Furthermore, up to 40 % of all patients with epilepsy cannot control their seizures with current medications. More efficacious treatments for medication refractory epilepsy are therefore needed. A better understanding of the mechanisms that cause this disorder is likely to facilitate the discovery of such treatments. Impairment in cerebral energy metabolism has been proposed as a possible causative factor in the pathogenesis of temporal lobe epilepsy (TLE), which is one of the most common types of medication-refractory epilepsies in adults. In this review, we will discuss some of the current hypotheses regarding the possible causal relationship between brain energy metabolism and TLE. Emphasis will be placed on the role of energy substrates (lactate and ketone bodies) and their transporter molecules, particularly monocarboxylate transporters 1 and 2 (MCT1 and MCT2). We recently reported that the cellular distribution of MCT1 and MCT2 is perturbed in the hippocampus in patients with TLE. The changes may be an adaptive response aimed at keeping high levels of lactate in the epileptic tissue, which may serve to counteract epileptic activity by downregulating cAMP levels through the lactate receptor GPR81, newly discovered in hippocampus. We propose that the perturbation of MCTs may be further involved in the pathophysiology of TLE by influencing brain energy homeostasis, mitochondrial function, GABA-ergic and glutamatergic neurotransmission, and flux of lactate through the brain.

  14. Monocarboxylate transporter 4 (MCT4) and CD147 overexpression is associated with poor prognosis in prostate cancer

    PubMed Central

    2011-01-01

    Background Monocarboxylate transporters (MCTs) are transmembrane proteins involved in the transport of monocarboxylates across the plasma membrane, which appear to play an important role in solid tumours, however the role of MCTs in prostate cancer is largely unknown. The aim of the present work was to evaluate the clinico-pathological value of monocarboxylate transporters (MCTs) expression, namely MCT1, MCT2 and MCT4, together with CD147 and gp70 as MCT1/4 and MCT2 chaperones, respectively, in prostate carcinoma. Methods Prostate tissues were obtained from 171 patients, who performed radical prostatectomy and 14 patients who performed cystoprostatectomy. Samples and clinico-pathological data were retrieved and organized into tissue microarray (TMAs) blocks. Protein expression was evaluated by immunohistochemistry in neoplastic (n = 171), adjacent non-neoplastic tissues (n = 135), PIN lesions (n = 40) and normal prostatic tissue (n = 14). Protein expression was correlated with patients' clinicopathologic characteristics. Results In the present study, a significant increase of MCT2 and MCT4 expression in the cytoplasm of tumour cells and a significant decrease in both MCT1 and CD147 expression in prostate tumour cells was observed when compared to normal tissue. All MCT isoforms and CD147 were expressed in PIN lesions. Importantly, for MCT2 and MCT4 the expression levels in PIN lesions were between normal and tumour tissue, which might indicate a role for these MCTs in the malignant transformation. Associations were found between MCT1, MCT4 and CD147 expressions and poor prognosis markers; importantly MCT4 and CD147 overexpression correlated with higher PSA levels, Gleason score and pT stage, as well as with perineural invasion and biochemical recurrence. Conclusions Our data provides novel evidence for the involvement of MCTs in prostate cancer. According to our results, we consider that MCT2 should be further explored as tumour marker and both MCT4 and CD147 as

  15. NO3 radical, OH radical and O3-initiated secondary aerosol formation from aliphatic amines

    NASA Astrophysics Data System (ADS)

    Tang, Xiaochen; Price, Derek; Praske, Eric; Lee, Su Anne; Shattuck, Morgan A.; Purvis-Roberts, Kathleen; Silva, Philip J.; Asa-Awuku, Akua; Cocker, David R.

    2013-06-01

    Aliphatic amines enter the atmosphere from a variety of sources, and exist in both gas and particle phases in the atmosphere. Similar to ammonia, amines can form inorganic salts through acid-base reactions. However, the atmospheric behavior of amines with atmospheric oxidants (e.g. the nitrate radical (NO3), the hydroxyl radical (OH), O3) is still poorly understood. In this study, chamber experiments were conducted to explore the reaction between three aliphatic amines and HNO3/O3/NO3/OH. Effects of water vapor were also explored by conducting experiments under different relative humidity conditions (RH<0.1% to ˜40%). Results show that all three amines have a high potential to form secondary aerosol in reactions with NO3, and are affected by the presence of water vapor. DEA and BA are capable of forming a significant amount of stable inorganic salt at ppb level concentrations, while TMA tends to form mostly non-salt secondary organic aerosol under dry conditions. The OH photooxidation of amines has much lower secondary aerosol yield and is independent of relative humidity, while ozonolysis produced negligible amount of aerosol. Secondary aerosol from OH oxidation was composed of organic components only, due to the lack of acid source. This study shows that night time chemistry of aliphatic amines can produce secondary organic and inorganic aerosol mixtures, and the relative contribution of each component depends on the environment relative humidity.

  16. Adsorption of halogenated aliphatic contaminants by graphene nanomaterials.

    PubMed

    Zhou, Yang; Apul, Onur Guven; Karanfil, Tanju

    2015-08-01

    In this study, adsorption of ten environmentally halogenated aliphatic synthetic organic compounds (SOCs) by a pristine graphene nanosheet (GNS) and a reduced graphene oxide (rGO) was examined, and their adsorption behaviors were compared with those of a single-walled carbon nanotube (SWCNT) and a granular activated carbon (GAC). In addition, the impacts of background water components (i.e., natural organic matter (NOM), ionic strength (IS) and pH) on the SOC adsorption behavior were investigated. The results indicated HD3000 and SWCNT with higher microporous volumes exhibited higher adsorption capacities for the selected aliphatic SOCs than graphenes, demonstrating microporosity of carbonaceous adsorbents played an important role in the adsorption. Analysis of adsorption isotherms demonstrated that hydrophobic interactions were the dominant contributor to the adsorption of aliphatic SOCs by graphenes. However, π-π electron donor-acceptor and van der Waals interactions are likely the additional mechanisms contributing to the adsorption of aliphatic SOCs on graphenes. Among the three background solution components examined, NOM showed the most influential effect on adsorption of the selected aliphatic SOCs, while pH and ionic strength had a negligible effects. The NOM competition on aliphatic adsorption was less pronounced on graphenes than SWCNT. Overall, in terms of adsorption capacities, graphenes tested in this study did not exhibit a major advantage over SWCNT and GAC for the adsorption of aliphatic SOCs.

  17. Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes

    PubMed Central

    Vida, Norbert; Václavík, Jiří

    2016-01-01

    Summary Oxidation of 3- and 4-pentafluorosulfanyl-substituted anisoles and phenols with hydrogen peroxide and sulfuric acid provided a mixture of SF5-substituted muconolactone, maleic, and succinic acids. A plausible mechanism for the formation of the aliphatic SF5 compounds was presented and their chemical reactivity was investigated. SF5-substituted para-benzoquinone was synthesized; its oxidation led to an improved yield of 2-(pentafluorosulfanyl)maleic acid. The reaction of SF5-substituted maleic anhydride and para-benzoquinone with cyclopentadiene afforded the Diels–Alder adducts. Decomposition of 3-(pentafluorosulfanyl)muconolactone in acidic, neutral and basic aqueous media was investigated and the decarboxylation of 2-(pentafluorosulfanyl)maleic acid provided 3-(pentafluorosulfanyl)acrylic acid. PMID:26877813

  18. Synthesis and reactivity of aliphatic sulfur pentafluorides from substituted (pentafluorosulfanyl)benzenes.

    PubMed

    Vida, Norbert; Václavík, Jiří; Beier, Petr

    2016-01-01

    Oxidation of 3- and 4-pentafluorosulfanyl-substituted anisoles and phenols with hydrogen peroxide and sulfuric acid provided a mixture of SF5-substituted muconolactone, maleic, and succinic acids. A plausible mechanism for the formation of the aliphatic SF5 compounds was presented and their chemical reactivity was investigated. SF5-substituted para-benzoquinone was synthesized; its oxidation led to an improved yield of 2-(pentafluorosulfanyl)maleic acid. The reaction of SF5-substituted maleic anhydride and para-benzoquinone with cyclopentadiene afforded the Diels-Alder adducts. Decomposition of 3-(pentafluorosulfanyl)muconolactone in acidic, neutral and basic aqueous media was investigated and the decarboxylation of 2-(pentafluorosulfanyl)maleic acid provided 3-(pentafluorosulfanyl)acrylic acid. PMID:26877813

  19. Physical Exercise–Induced Hypoglycemia Caused by Failed Silencing of Monocarboxylate Transporter 1 in Pancreatic β Cells

    PubMed Central

    Otonkoski, Timo ; Jiao, Hong ; Kaminen-Ahola, Nina ; Tapia-Paez, Isabel ; Ullah, Mohammed S. ; Parton, Laura E. ; Schuit, Frans ; Quintens, Roel ; Sipilä, Ilkka ; Mayatepek, Ertan ; Meissner, Thomas ; Halestrap, Andrew P. ; Rutter, Guy A. ; Kere, Juha 

    2007-01-01

    Exercise-induced hyperinsulinism (EIHI) is a dominantly inherited hypoglycemic disorder characterized by inappropriate insulin secretion during anaerobic exercise or on pyruvate load. We aimed to identify the molecular basis of this novel disorder of β-cell regulation. EIHI mapped to chromosome 1 (LOD score 3.6) in a genome scan performed for two families with 10 EIHI-affected patients. Mutational analysis of the promoter of the SLC16A1 gene, which encodes monocarboxylate transporter 1 (MCT1), located under the linkage peak, revealed changes in all 13 identified patients with EIHI. Patient fibroblasts displayed abnormally high SLC16A1 transcript levels, although monocarboxylate transport activities were not changed in these cells, reflecting additional posttranscriptional control of MCT1 levels in extrapancreatic tissues. By contrast, when examined in β cells, either of two SLC16A1 mutations identified in separate pedigrees resulted in increased protein binding to the corresponding promoter elements and marked (3- or 10-fold) transcriptional stimulation of SLC16A1 promoter-reporter constructs. These studies show that promoter-activating mutations in EIHI induce SLC16A1 expression in β cells, where this gene is not usually transcribed, permitting pyruvate uptake and pyruvate-stimulated insulin release despite ensuing hypoglycemia. These findings describe a novel disease mechanism based on the failure of cell-specific transcriptional silencing of a gene that is highly expressed in other tissues. PMID:17701893

  20. ANAEROBIC AND AEROBIC TREATMENT OF CHLORINATED ALIPHATIC COMPOUNDS

    EPA Science Inventory

    Biological degradation of 12 chlorinated aliphatic compounds (CACs) was assessed in bench-top reactors and in serum bottle tests. Three continuously mixed daily batch-fed reactor systems were evaluated: anaerobic, aerobic, and sequential-anaerobic-aerobic (sequential). Glucose,...

  1. Phenylethanoid and aliphatic alcohol glycosides from Acanthus ilicifolius.

    PubMed

    Wu, Jun; Zhang, Si; Xiao, Qiang; Li, Qingxin; Huang, Jianshe; Long, Lijuan; Huang, Liangmin

    2003-06-01

    A phenylethanoid glycoside (ilicifolioside A) and an aliphatic alcohol glycoside (ilicifolioside B), have been isolated from the aerial parts of Acanthus ilicifolius, together with eight known compounds. Their structures were determined from spectroscopic analyses.

  2. Age-Dependent Changes of Monocarboxylate Transporter 8 Availability in the Postnatal Murine Retina.

    PubMed

    Henning, Yoshiyuki; Szafranski, Karol

    2016-01-01

    The thyroid hormones (TH) triiodothyronine (T3) and its prohormone thyroxine (T4) are crucial for retinal development and function, and increasing evidence points at TH dysregulation as a cause for retinal degenerative diseases. Thus, precise regulation of retinal TH supply is required for proper retinal function, but knowledge on these mechanisms is still fragmentary. Several transmembrane transporters have been described as key regulators of TH availability in target tissues of which the monocarboxylate transporter 8 (MCT8), a high affinity transporter for T4 and T3, plays an essential role in the central nervous system. Moreover, in the embryonic chicken retina, MCT8 is highly expressed, but the postnatal availability of MCT8 in the mammalian retina was not reported to date. In the present study, spatiotemporal retinal MCT8 availability was examined in mice of different age. For this purpose, we quantified expression levels of Mct8 via Real-Time Reverse-Transcriptase PCR in mouse eyecups (C57BL/6) of juvenile and adult age groups. Additionally, age-dependent MCT8 protein levels were quantified via Western blotting and localized via immunofluorescence confocal microscopy. While no difference in Mct8 expression levels could be detected between age groups, MCT8 protein levels in juvenile animals were about two times higher than in adult animals based on Western blot analyses. Immunohistochemical analyses showed that MCT8 immunoreactivity in the eyecup was restricted to the retina and the retinal pigment epithelium. In juvenile mice, MCT8 was broadly observed along the apical membrane of the retinal pigment epithelium, tightly surrounding photoreceptor outer segments. Distinct immunopositive staining was also detected in the inner nuclear layer and the ganglion cell layer. However, in adult specimens, immunoreactivity visibly declined in all layers, which was in line with Western blot analyses. Since MCT8 was abundantly present in juvenile and about twofold lower in

  3. Age-Dependent Changes of Monocarboxylate Transporter 8 Availability in the Postnatal Murine Retina

    PubMed Central

    Henning, Yoshiyuki; Szafranski, Karol

    2016-01-01

    The thyroid hormones (TH) triiodothyronine (T3) and its prohormone thyroxine (T4) are crucial for retinal development and function, and increasing evidence points at TH dysregulation as a cause for retinal degenerative diseases. Thus, precise regulation of retinal TH supply is required for proper retinal function, but knowledge on these mechanisms is still fragmentary. Several transmembrane transporters have been described as key regulators of TH availability in target tissues of which the monocarboxylate transporter 8 (MCT8), a high affinity transporter for T4 and T3, plays an essential role in the central nervous system. Moreover, in the embryonic chicken retina, MCT8 is highly expressed, but the postnatal availability of MCT8 in the mammalian retina was not reported to date. In the present study, spatiotemporal retinal MCT8 availability was examined in mice of different age. For this purpose, we quantified expression levels of Mct8 via Real-Time Reverse-Transcriptase PCR in mouse eyecups (C57BL/6) of juvenile and adult age groups. Additionally, age-dependent MCT8 protein levels were quantified via Western blotting and localized via immunofluorescence confocal microscopy. While no difference in Mct8 expression levels could be detected between age groups, MCT8 protein levels in juvenile animals were about two times higher than in adult animals based on Western blot analyses. Immunohistochemical analyses showed that MCT8 immunoreactivity in the eyecup was restricted to the retina and the retinal pigment epithelium. In juvenile mice, MCT8 was broadly observed along the apical membrane of the retinal pigment epithelium, tightly surrounding photoreceptor outer segments. Distinct immunopositive staining was also detected in the inner nuclear layer and the ganglion cell layer. However, in adult specimens, immunoreactivity visibly declined in all layers, which was in line with Western blot analyses. Since MCT8 was abundantly present in juvenile and about twofold lower in

  4. 3-bromopyruvate enhanced daunorubicin-induced cytotoxicity involved in monocarboxylate transporter 1 in breast cancer cells.

    PubMed

    Liu, Zhe; Sun, Yiming; Hong, Haiyu; Zhao, Surong; Zou, Xue; Ma, Renqiang; Jiang, Chenchen; Wang, Zhiwei; Li, Huabin; Liu, Hao

    2015-01-01

    Increasing evidence demonstrates that the hexokinase inhibitor 3-bromopyruvate (3-BrPA) induces the cell apoptotic death by inhibiting ATP generation in human cancer cells. Interestingly, some tumor cell lines are less sensitive to 3-BrPA-induced apoptosis than others. Moreover, the molecular mechanism of 3-BrPA-trigged apoptosis is unclear. In the present study, we examined the effects of 3-BrPA on the viability of the breast cancer cell lines MDA-MB-231 and MCF-7. We further investigated the potential roles of monocarboxylate transporter 1 (MCT1) in drug accumulation and efflux of breast cancer cells. Finally, we explored whether 3-BrPA enhanced daunorubicin (DNR)-induced cytotoxicity through regulation of MCT1 in breast cancer cells. MTT and colony formation assays were used to measure cell viability. Western blot analysis, flow cytometric analysis and fluorescent microscopy were used to determine the molecular mechanism of actions of MCT1 in different breast cancer cell lines. Whole-body bioluminescence imaging was used to investigate the effect of 3-BrPA in vivo. We found that 3-BrPA significantly inhibited cell growth and induced apoptosis in MCF-7 cell line, but not in MDA-MB-231 cells. Moreover, we observed that 3-BrPA efficiently enhanced DNR-induced cytotoxicity in MCF-7 cells by inhibiting the activity of ATP-dependent efflux pumps. We also found that MCT1 overexpression increased the efficacy of 3-BrPA in MDA-MB-231 cells. 3-BrPA markedly suppressed subcutaneous tumor growth in combination with DNR in nude mice implanted with MCF-7 cells. Lastly, our whole-body bioluminescence imaging data indicated that 3-BrPA promoted DNR accumulation in tumors. These findings collectively suggest that 3-BrPA enhanced DNR antitumor activity in breast cancer cells involved MCT-1, suggesting that inhibition of glycolysis could be an effective therapeutic approach for breast cancer treatment. PMID:26609475

  5. Age-Dependent Changes of Monocarboxylate Transporter 8 Availability in the Postnatal Murine Retina

    PubMed Central

    Henning, Yoshiyuki; Szafranski, Karol

    2016-01-01

    The thyroid hormones (TH) triiodothyronine (T3) and its prohormone thyroxine (T4) are crucial for retinal development and function, and increasing evidence points at TH dysregulation as a cause for retinal degenerative diseases. Thus, precise regulation of retinal TH supply is required for proper retinal function, but knowledge on these mechanisms is still fragmentary. Several transmembrane transporters have been described as key regulators of TH availability in target tissues of which the monocarboxylate transporter 8 (MCT8), a high affinity transporter for T4 and T3, plays an essential role in the central nervous system. Moreover, in the embryonic chicken retina, MCT8 is highly expressed, but the postnatal availability of MCT8 in the mammalian retina was not reported to date. In the present study, spatiotemporal retinal MCT8 availability was examined in mice of different age. For this purpose, we quantified expression levels of Mct8 via Real-Time Reverse-Transcriptase PCR in mouse eyecups (C57BL/6) of juvenile and adult age groups. Additionally, age-dependent MCT8 protein levels were quantified via Western blotting and localized via immunofluorescence confocal microscopy. While no difference in Mct8 expression levels could be detected between age groups, MCT8 protein levels in juvenile animals were about two times higher than in adult animals based on Western blot analyses. Immunohistochemical analyses showed that MCT8 immunoreactivity in the eyecup was restricted to the retina and the retinal pigment epithelium. In juvenile mice, MCT8 was broadly observed along the apical membrane of the retinal pigment epithelium, tightly surrounding photoreceptor outer segments. Distinct immunopositive staining was also detected in the inner nuclear layer and the ganglion cell layer. However, in adult specimens, immunoreactivity visibly declined in all layers, which was in line with Western blot analyses. Since MCT8 was abundantly present in juvenile and about twofold lower in

  6. Evaluation of antibacterial activity of synthetic aliphatic and aromatic monoacylglycerols.

    PubMed

    Batovska, Daniela; Todorova, Iva; Parushev, Stoyan; Tsvetkova, Iva; Najdenski, Hristo; Ubukata, Makoto

    2008-01-01

    The antibacterial activity of synthetic aliphatic and aromatic monoacylglycerols (MAGs) was studied against two human pathogens: Staphylococcus aureus and Escherichia coli. The active compounds inhibited selectively S. aureus. The most active compounds amongst them were those with medium size aliphatic chain and aromatic MAGs with electron withdrawing substituents at the aryl ring. The introduction of one or two-carbon spacer between the aryl ring and the carboxylic function did not influence antibacterial effectiveness. PMID:19004249

  7. Olfactory discrimination ability for aliphatic esters in squirrel monkeys and humans.

    PubMed

    Laska, M; Freyer, D

    1997-08-01

    Using a behavioral paradigm designed to simulate olfactory-guided foraging, the ability of five squirrel monkeys to distinguish iso-amyl acetate from n- and iso-forms of other acetic esters (ethyl acetate to decyl acetate) and from other esters carrying the iso-amyl group (iso-amyl propionate to iso-amyl capronate) was investigated. We found (i) that all five animals were clearly able to discriminate between all odor pairs tested; (ii) a significant negative correlation between discrimination performance and structural similarity of odorants in terms of differences in carbon chain length of both the aliphatic alcohol group and the aliphatic acid group of the esters; and (iii) that iso- and n-amyl acetate were perceived as qualitatively similar despite different steric conformation. Using a triple-forced choice procedure, 20 human subjects were tested on the same tasks in parallel and showed a very similar pattern of discrimination performance compared with the squirrel monkeys. Thus, the results of this study provide evidence of well-developed olfactory discrimination ability in squirrel monkeys for aliphatic esters and support the assumption that human and non-human primates may share common principles of odor quality perception. PMID:9279468

  8. A novel mutation in the monocarboxylate transporter 8 gene in a boy with putamen lesions and low free T4 levels in cerebrospinal fluid.

    PubMed

    Kakinuma, Hiroaki; Itoh, Masatsune; Takahashi, Hiroaki

    2005-10-01

    We describe brain lesions in a patient with a monocarboxylate transporter 8 mutation. Imaging showed a high T2 lesion in the left putamen at age 3 and a right putamen lesion at age 6. Cerebrospinal fluid free thyroxine concentrations were low, with normal 3,3',5-triiodothyronine concentrations.

  9. Topsoil drying combined with increased sulfur supply leads to enhanced aliphatic glucosinolates in Brassica juncea leaves and roots.

    PubMed

    Tong, Yu; Gabriel-Neumann, Elke; Ngwene, Benard; Krumbein, Angelika; George, Eckhard; Platz, Stefanie; Rohn, Sascha; Schreiner, Monika

    2014-01-01

    The decrease of water availability is leading to an urgent demand to reduce the plants' water supply. This study evaluates the effect of topsoil drying, combined with varying sulfur (S) supply on glucosinolates in Brassica juncea in order to reveal whether a partial root drying may already lead to a drought-induced glucosinolate increase promoted by an enhanced S supply. Without decreasing biomass, topsoil drying initiated an increase in aliphatic glucosinolates in leaves and in topsoil dried roots supported by increased S supply. Simultaneously, abscisic acid was determined, particularly in dehydrated roots, associated with an increased abscisic acid concentration in leaves under topsoil drying. This indicates that the dehydrated roots were the direct interface for the plants' stress response and that the drought-induced accumulation of aliphatic glucosinolates is related to abscisic acid formation. Indole and aromatic glucosinolates decreased, suggesting that these glucosinolates are less involved in the plants' response to drought. PMID:24444925

  10. Aliphatic chain length by isotropic mixing (ALCHIM): determining composition of complex lipid samples by 1H NMR spectroscopy

    PubMed Central

    Yi, Ruiyang; Volden, Paul A.; Conzen, Suzanne D.

    2015-01-01

    Quantifying the amounts and types of lipids present in mixtures is important in fields as diverse as medicine, food science, and biochemistry. Nuclear magnetic resonance (NMR) spectroscopy can quantify the total amounts of saturated and unsaturated fatty acids in mixtures, but identifying the length of saturated fatty acid or the position of unsaturation by NMR is a daunting challenge. We have developed an NMR technique, aliphatic chain length by isotropic mixing, to address this problem. Using a selective total correlation spectroscopy technique to excite and transfer magnetization from a resolved resonance, we demonstrate that the time dependence of this transfer to another resolved site depends linearly on the number of aliphatic carbons separating the two sites. This technique is applied to complex natural mixtures allowing the identification and quantification of the constituent fatty acids. The method has been applied to whole adipocytes demonstrating that it will be of great use in studies of whole tissues. PMID:24831341

  11. SAMPLING ARTIFACT ESTIMATES FOR ALKANES, HOPANES, AND ALIPHATIC CARBOXYLIC ACIDS

    EPA Science Inventory

    Sampling artifacts for molecular markers from organic speciation of particulate matter were investigated by analyzing forty-one samples collected in Philadelphia as a part of the Northeast Oxidant and Particulate Study (NEOPS). Samples were collected using a high volume sampler ...

  12. Indigenous aliphatic amines in the aqueously altered Orgueil meteorite

    NASA Astrophysics Data System (ADS)

    Aponte, José C.; Dworkin, Jason P.; Elsila, Jamie E.

    2015-10-01

    The CI1 Orgueil meteorite is a highly aqueously altered carbonaceous chondrite. It has been extensively studied, and despite its extensive degree of aqueous alteration and some documented instances of contamination, several indigenous organic compounds including amino acids, carboxylic acids, and nucleobases have been detected in its carbon-rich matrix. We recently developed a novel gas chromatographic method for the enantiomeric and compound-specific isotopic analyses of meteoritic aliphatic monoamines in extracts and have now applied this method to investigate the monoamine content in Orgueil. We detected 12 amines in Orgueil, with concentrations ranging from 1.1 to 332 nmol g-1 of meteorite and compared this amine content in Orgueil with that of the CM2 Murchison meteorite, which experienced less parent-body aqueous alteration. Methylamine is four times more abundant in Orgueil than in Murchison. As with other species, the amine content in Orgueil extracts shows less structural diversity than that in Murchison extracts. We measured the compound-specific stable carbon isotopic ratios (δ13C) for 5 of the 12 monoamines detected in Orgueil and found a range of δ13C values from -20 to +59‰. These δ13C values fall into the range of other meteoritic organic compounds, although they are 13C-depleted relative to their counterparts extracted from the Murchison meteorite. In addition, we measured the enantiomeric composition for the chiral monoamines (R)- and (S)-sec-butylamine in Orgueil, and found it was racemic within experimental error, in contrast with the L-enantiomeric excess found for its amino acid structural analog isovaline. The racemic nature of sec-butylamine in Orgueil was comparable to that previously observed in Murchison, and to other CM2 and CR2 carbonaceous chondrites measured in this work (ALH 83100 [CM1/2], LON 94101 [CM2], LEW 90500 [CM2], LAP 02342 [CR2], and GRA 95229 [CR2]). These results allow us to place some constraints on the effects of

  13. Iron-Catalyzed Oxyfunctionalization of Aliphatic Amines at Remote Benzylic C-H Sites.

    PubMed

    Mbofana, Curren T; Chong, Eugene; Lawniczak, James; Sanford, Melanie S

    2016-09-01

    We report the development of an iron-catalyzed method for the selective oxyfunctionalization of benzylic C(sp(3))-H bonds in aliphatic amine substrates. This transformation is selective for benzylic C-H bonds that are remote (i.e., at least three carbons) from the amine functional group. High site selectivity is achieved by in situ protonation of the amine with trifluoroacetic acid, which deactivates more traditionally reactive C-H sites that are α to nitrogen. The scope and synthetic utility of this method are demonstrated via the synthesis and derivatization of a variety of amine-containing, biologically active molecules. PMID:27529646

  14. Aliphatic alcohols in spirits inhibit phagocytosis by human monocytes.

    PubMed

    Pál, László; Árnyas, Ervin M; Bujdosó, Orsolya; Baranyi, Gergő; Rácz, Gábor; Ádány, Róza; McKee, Martin; Szűcs, Sándor

    2015-04-01

    A large volume of alcoholic beverages containing aliphatic alcohols is consumed worldwide. Previous studies have confirmed the presence of ethanol-induced immunosuppression in heavy drinkers, thereby increasing susceptibility to infectious diseases. However, the aliphatic alcohols contained in alcoholic beverages might also impair immune cell function, thereby contributing to a further decrease in microbicidal activity. Previous research has shown that aliphatic alcohols inhibit phagocytosis by granulocytes but their effect on human monocytes has not been studied. This is important as they play a crucial role in engulfment and killing of pathogenic microorganisms and a decrease in their phagocytic activity could lead to impaired antimicrobial defence in heavy drinkers. The aim of this study was to measure monocyte phagocytosis following their treatment with those aliphatic alcohols detected in alcoholic beverages. Monocytes were separated from human peripheral blood and phagocytosis of opsonized zymosan particles by monocytes treated with ethanol and aliphatic alcohols individually and in combination was determined. It was shown that these alcohols could suppress the phagocytic activity of monocytes in a concentration-dependent manner and when combined with ethanol, they caused a further decrease in phagocytosis. Due to their additive effects, it is possible that they may inhibit phagocytosis in a clinically meaningful way in alcoholics and episodic heavy drinkers thereby contribute to their increased susceptibility to infectious diseases. However, further research is needed to address this question.

  15. Hyperbranched Aliphatic Polyester Modified Activated Carbon Particles with Homogenized Surface Groups

    NASA Astrophysics Data System (ADS)

    Liu, Peng; Zhang, Liuxue

    The hyperbranched aliphatic polyester grafted activated carbon (HAPE-AC), was successfully prepared by the simple "one-pot" method. The surface functional groups of commercial activated carbon particles were homogenized to hydroxyl groups by being oxidized with nitric acid and then reduced with lithium tetrahydroaluminate (LiAlH4) at first. Secondly, the surface hydroxyl groups were used as the active sites for the solution polycondensation of the AB2 monomer, 2, 2-bis(hydroxymethyl)propionic acid (bis-MPA), with the catalysis of p-toluenesulfonic acid (p-TSA). The homogenization of the surface groups of the activated carbon particles and the graft polymerization of the hyperbranched aliphatic polyester were investigated by X-ray photoelectron spectroscopy (XPS) technique. The products were also characterized with Fourier transform infrared (FT-IR) and scanning electron microscope (SEM). The competitive adsorption properties of the products toward the heavy metal ions (Cu(II), Hg(II), Zn(II), and Cd(II)) also proved the translations of the surface groups.

  16. Composition and sources of aliphatic lipids and sterols in sediments of a tropical island, southern South China Sea: preliminary assessment.

    PubMed

    Mohd Tahir, N; Pang, S Y; Abdullah, N A; Suratman, S

    2013-12-01

    Near-shore surface sediment was collected from five stations off Redang Island located on the eastern coast of Peninsular Malaysia. Freeze-dried sediments were Soxhlet extracted and then fractionated using column chromatography into aliphatic and polar fractions. Determination of these fractions was carried out using gas chromatography mass spectrometry. The concentration of total resolved aliphatic hydrocarbons in sediments ranged from 157 to 308 ng/g. The distribution of aliphatic fraction showed the presence of n-alkanes ranging from nC15 to nC33 with a minor odd-to-even predominance exhibiting carbon maximum, depending on station, at nC17, nC26, nC29 or nC31. Calculation of Carbon Preference Index (CPI) for CPI(15-33) gave values ranging from 1.09 to 1.46. n-Alkanol in all sediment exhibits even-to-odd carbon predominance ranging from nC16 to nC28 and maximising at nC22. n-Fatty acids distribution ranged from nC14 to nC24 with a dominant maximum at nC16 and exhibiting high values of short chain fatty acids (≤nC20) to long chain fatty acids (>nC20) ratios. Unsaturated fatty acids, particularly nC16:1 and nC18:1 is also ubiquitous in all samples. Cholesterol is the most abundant compound amongst the sterol group ranging from 42.8 to 62.6% of the total sterols. β-Sitosterol, brassicasterol and stigmasterol, are also present but of relatively lower amount. These observations suggest that the aliphatic lipids and sterols in the study area originate, mainly, from biogenic sources of marine microbial with minor contribution from epiticular waxes of terrestrial plants.

  17. Composition and sources of aliphatic lipids and sterols in sediments of a tropical island, southern South China Sea: preliminary assessment.

    PubMed

    Mohd Tahir, N; Pang, S Y; Abdullah, N A; Suratman, S

    2013-12-01

    Near-shore surface sediment was collected from five stations off Redang Island located on the eastern coast of Peninsular Malaysia. Freeze-dried sediments were Soxhlet extracted and then fractionated using column chromatography into aliphatic and polar fractions. Determination of these fractions was carried out using gas chromatography mass spectrometry. The concentration of total resolved aliphatic hydrocarbons in sediments ranged from 157 to 308 ng/g. The distribution of aliphatic fraction showed the presence of n-alkanes ranging from nC15 to nC33 with a minor odd-to-even predominance exhibiting carbon maximum, depending on station, at nC17, nC26, nC29 or nC31. Calculation of Carbon Preference Index (CPI) for CPI(15-33) gave values ranging from 1.09 to 1.46. n-Alkanol in all sediment exhibits even-to-odd carbon predominance ranging from nC16 to nC28 and maximising at nC22. n-Fatty acids distribution ranged from nC14 to nC24 with a dominant maximum at nC16 and exhibiting high values of short chain fatty acids (≤nC20) to long chain fatty acids (>nC20) ratios. Unsaturated fatty acids, particularly nC16:1 and nC18:1 is also ubiquitous in all samples. Cholesterol is the most abundant compound amongst the sterol group ranging from 42.8 to 62.6% of the total sterols. β-Sitosterol, brassicasterol and stigmasterol, are also present but of relatively lower amount. These observations suggest that the aliphatic lipids and sterols in the study area originate, mainly, from biogenic sources of marine microbial with minor contribution from epiticular waxes of terrestrial plants. PMID:23856812

  18. Catalytic Asymmetric Hydroamination of Unactivated Internal Olefins to Aliphatic Amines

    PubMed Central

    Yang, Yang; Shi, Shi-Liang; Niu, Dawen; Liu, Peng; Buchwald, Stephen L.

    2015-01-01

    Catalytic assembly of enantiopure aliphatic amines from abundant and readily available precursors has long been recognized as a paramount challenge in synthetic chemistry. Herein, we describe a mild and general copper-catalyzed hydroamination that effectively converts unactivated internal olefins, an important yet unexploited class of abundant feedstock chemicals, into highly enantioenriched α-branched amines (≥ 96% enantiomeric excess) featuring two minimally differentiated aliphatic substituents. This method provides a powerful means to access a broad range of advanced, highly functionalized enantioenriched amines of interest in pharmaceutical research and other areas. PMID:26138973

  19. Applicability of the theory of thermodynamic similarity to predict the enthalpies of vaporization of aliphatic aldehydes

    NASA Astrophysics Data System (ADS)

    Esina, Z. N.; Korchuganova, M. R.

    2015-06-01

    The theory of thermodynamic similarity is used to predict the enthalpies of vaporization of aliphatic aldehydes. The predicted data allow us to calculate the phase diagrams of liquid-vapor equilibrium in a binary water-aliphatic aldehyde system.

  20. Selective stabilization of aliphatic organic carbon by iron oxide

    PubMed Central

    Adhikari, Dinesh; Yang, Yu

    2015-01-01

    Stabilization of organic matter in soil is important for natural ecosystem to sequestrate carbon and mitigate greenhouse gas emission. It is largely unknown what factors govern the preservation of organic carbon in soil, casting shadow on predicting the response of soil to climate change. Iron oxide was suggested as an important mineral preserving soil organic carbon. However, ferric minerals are subject to reduction, potentially releasing iron and decreasing the stability of iron-bound organic carbon. Information about the stability of iron-bound organic carbon in the redox reaction is limited. Herein, we investigated the sorptive interactions of organic matter with hematite and reductive release of hematite-bound organic matter. Impacts of organic matter composition and conformation on its sorption by hematite and release during the reduction reaction were analyzed. We found that hematite-bound aliphatic carbon was more resistant to reduction release, although hematite preferred to sorb more aromatic carbon. Resistance to reductive release represents a new mechanism that aliphatic soil organic matter was stabilized by association with iron oxide. Selective stabilization of aliphatic over aromatic carbon can greatly contribute to the widely observed accumulation of aliphatic carbon in soil, which cannot be explained by sorptive interactions between minerals and organic matter. PMID:26061259

  1. Triphosgene–Amine Base Promoted Chlorination of Unactivated Aliphatic Alcohols

    PubMed Central

    Villalpando, Andrés; Ayala, Caitlan E.; Watson, Christopher B.; Kartika, Rendy

    2014-01-01

    Unactivated α-branched primary and secondary aliphatic alcohols have been successfully transformed into their corresponding alkyl chlorides in high yields upon treatment with a mixture of triphosgene and pyridine in dichloromethane at reflux. These mild chlorination conditions are high yielding, stereospecific, and well tolerated by numerous sensitive functionalities. Furthermore, no nuisance waste products are generated in the course of the reactions. PMID:23496045

  2. Cloud condensation nuclei activity of aliphatic amine secondary aerosol

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g. hydroxyl radical and nitrate radical). The resulting particle composition can contain both secondary organic aerosol (SOA) and inorganic salts. The fraction of organic to inorganic materials in the particulate ...

  3. Selective stabilization of aliphatic organic carbon by iron oxide.

    PubMed

    Adhikari, Dinesh; Yang, Yu

    2015-01-01

    Stabilization of organic matter in soil is important for natural ecosystem to sequestrate carbon and mitigate greenhouse gas emission. It is largely unknown what factors govern the preservation of organic carbon in soil, casting shadow on predicting the response of soil to climate change. Iron oxide was suggested as an important mineral preserving soil organic carbon. However, ferric minerals are subject to reduction, potentially releasing iron and decreasing the stability of iron-bound organic carbon. Information about the stability of iron-bound organic carbon in the redox reaction is limited. Herein, we investigated the sorptive interactions of organic matter with hematite and reductive release of hematite-bound organic matter. Impacts of organic matter composition and conformation on its sorption by hematite and release during the reduction reaction were analyzed. We found that hematite-bound aliphatic carbon was more resistant to reduction release, although hematite preferred to sorb more aromatic carbon. Resistance to reductive release represents a new mechanism that aliphatic soil organic matter was stabilized by association with iron oxide. Selective stabilization of aliphatic over aromatic carbon can greatly contribute to the widely observed accumulation of aliphatic carbon in soil, which cannot be explained by sorptive interactions between minerals and organic matter. PMID:26061259

  4. Introducing Aliphatic Substitution with a Discovery Experiment Using Competing Electrophiles

    ERIC Educational Resources Information Center

    Curran, Timothy P.; Mostovoy, Amelia J.; Curran, Margaret E.; Berger, Clara

    2016-01-01

    A facile, discovery-based experiment is described that introduces aliphatic substitution in an introductory undergraduate organic chemistry curriculum. Unlike other discovery-based experiments that examine substitution using two competing nucleophiles with a single electrophile, this experiment compares two isomeric, competing electrophiles…

  5. A thermostable transketolase evolved for aliphatic aldehyde acceptors.

    PubMed

    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

  6. A novel chiral aliphatic-aromatic diamine promoted direct, highly enantio- and diastereoselective Michael addition of cyclohexanone to nitroolefins under solvent-free conditions.

    PubMed

    Miao, Shifeng; Bai, Jinjin; Yang, Jin; Zhang, Yawen

    2010-10-01

    A series of new highly efficient chiral aliphatic-aromatic diamine catalysts have been designed and successfully applied to the asymmetric Michael addition of cyclohexanone with nitroolefins under solvent-free conditions without any acidic additives. The desired adducts were obtained in high yields with excellent enantio- and diastereoselectivities of syn products (up to >99% ee, >99:1 dr).

  7. 40 CFR 721.10608 - Aliphatic diisocyanate polymer with alkanediol and alkylglycol (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Aliphatic diisocyanate polymer with... Significant New Uses for Specific Chemical Substances § 721.10608 Aliphatic diisocyanate polymer with.... (1) The chemical substance identified generically as aliphatic diisocyanate polymer with...

  8. 40 CFR 721.10608 - Aliphatic diisocyanate polymer with alkanediol and alkylglycol (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Aliphatic diisocyanate polymer with... Significant New Uses for Specific Chemical Substances § 721.10608 Aliphatic diisocyanate polymer with.... (1) The chemical substance identified generically as aliphatic diisocyanate polymer with...

  9. 40 CFR 721.7250 - Polyaziridinyl ester of an aliphatic alcohol (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Polyaziridinyl ester of an aliphatic... Specific Chemical Substances § 721.7250 Polyaziridinyl ester of an aliphatic alcohol (generic). (a... generically as a polyaziridinyl ester of an aliphatic alcohol (PMN P-01-97) is subject to reporting under...

  10. Compositions and sources of extractable organic matter in Mesopotamian marshland surface sediments of Iraq. I: aliphatic lipids

    NASA Astrophysics Data System (ADS)

    Rushdi, Ahmed I.; Douabul, Ali A.; Mohammed, Sama Samir; Simoneit, Bernd R. T.

    2006-08-01

    Shallow surface sediment samples from the Mesopotamian marshlands of Iraq were collected and analyzed to determine the distribution, concentrations and sources of aliphatic lipid compounds ( n-alkanes, n-alkanols, n-alkanoic acids, and methyl n-alkanoates) and molecular markers of petroleum in these wetlands. The sediments were collected using a stainless steel sediment corer, dried, extracted with a dichloromethane/methanol mixture and then analyzed by gas chromatography-mass spectrometry (GC MS). The aliphatic lipid compounds included n-alkanes, n-alkanoic acids, n-alkanols and methyl n-alkanoates with concentrations ranged from 6.8 to 31.1 μg/g, 4.1 to 5.0 μg/g, 5.9 to 7.7 μg/g and from 0.3 to 5.9 μg/g, respectively. The major sources of aliphatic lipids were natural from waxes of higher plants (24 30%) and microbial residues (42 30%), with a significant contribution from anthropogenic sources (27 30%, petroleum), based on the organic geochemical parameters and indices. Further studies are needed to characterize the rate, accumulation and transformation of various organic matter sources before and after re-flooding of these wetlands.

  11. One- and two-dimensional divalent copper coordination polymers based on kinked organodiimine and long flexible aliphatic dicarboxylate ligands

    NASA Astrophysics Data System (ADS)

    Mallika Krishnan, Subhashree; Supkowski, Ronald M.; LaDuca, Robert L.

    2008-11-01

    Hydrothermal synthesis under acidic conditions has afforded a pair of divalent copper coordination polymers containing the kinked dipodal tethering organodiimine 4,4'-dipyridylamine (dpa) and flexible long-chain aliphatic dicarboxylate ligands. The new materials were characterized by single crystal X-ray structure determination, infrared spectroscopy, and thermogravimetric analysis. [CuCl(suberate) 0.5(dpa)] ( 1) manifests 1-D ladder-like motifs aggregated into 3-D through hydrogen bonding and copper-mediated supramolecular interactions. Extension of the aliphatic chain within the dicarboxylate ligand by one methylene unit resulted in {[Cu(azelate)(dpa)(H 2O)] · 3H 2O} ( 2), a (4,4) rhomboid grid 2-D coordination polymer encapsulating acyclic water molecule trimers.

  12. Biodegradation of Aliphatic-Aromatic Copolyesters by Thermomonospora fusca and Other Thermophilic Compost Isolates

    PubMed Central

    Kleeberg, Ilona; Hetz, Claudia; Kroppenstedt, Reiner Michael; Müller, Rolf-Joachim; Deckwer, Wolf-Dieter

    1998-01-01

    Random aliphatic-aromatic copolyesters synthesized from 1,4-butanediol, adipic acid, and terephthalic acid (BTA) have excellent thermal and mechanical properties and are biodegradable by mixed cultures (e.g., in compost). Over 20 BTA-degrading strains were isolated by using compost as a microbial source. Among these microorganisms, thermophilic actinomycetes obviously play an outstanding role and appear to dominate the initial degradation step. Two actinomycete strains exhibited about 20-fold higher BTA degradation rates than usually observed in a common compost test. These isolates were identified as Thermomonospora fusca strains. They appeared to be particularly suitable for establishment of rapid degradation tests and were used in comparative studies on the biodegradation of various polyesters. PMID:9572944

  13. Analysis of aliphatic waxes associated with root periderm or exodermis from eleven plant species.

    PubMed

    Kosma, Dylan K; Rice, Adam; Pollard, Mike

    2015-09-01

    Aliphatic waxes can be found in association with suberized tissues, including roots. Non-polar lipids were isolated by rapid solvent extraction of mature regions of intact roots from eleven angiosperms, including both monocots and dicots. The majority of roots analyzed were taproots or tuberous taproots that had undergone secondary growth and thus were covered by a suberized periderm. The exceptions therein were maize (Zea mays L.) and rice (Oryza sativa L.), which present a suberized exodermis. The analysis herein focused on aliphatic waxes, with particular emphasis on alkyl hydroxycinnamates (AHCs). AHCs were widely distributed, absent from only one species, were found in both aerial and subterranean portions of tuberous taproots, and were associated with the fibrous roots of both maize and rice. Most species also contained monoacylglycerols, fatty alcohols and/or free fatty acids. Carrot (Daucus carrota L.) was the outlier, containing only free fatty acids, sterols, and polyacetylenes as identified components. Sterols were the only ubiquitous component across all roots analyzed. Monoacylglycerols of ω-hydroxy fatty acids were present in maize and rice root waxes. For species within the Brassiceae, wax compositions varied between subspecies or varieties and between aerial and subterranean portions of taproots. In addition, reduced forms of photo-oxidation products of ω-hydroxy oleate and its corresponding dicarboxylic acid (10,18-dihydroxy-octadec-8-enoate, 9,18-dihydroxy-octadec-10-enoate and 9-hydroxyoctadec-10-ene-1,18-dioate) were identified as naturally occurring suberin monomers in rutabaga (Brassica napus subsp. rapifera Metzg.) periderm tissues.

  14. Analysis of aliphatic waxes associated with root periderm or exodermis from eleven plant species.

    PubMed

    Kosma, Dylan K; Rice, Adam; Pollard, Mike

    2015-09-01

    Aliphatic waxes can be found in association with suberized tissues, including roots. Non-polar lipids were isolated by rapid solvent extraction of mature regions of intact roots from eleven angiosperms, including both monocots and dicots. The majority of roots analyzed were taproots or tuberous taproots that had undergone secondary growth and thus were covered by a suberized periderm. The exceptions therein were maize (Zea mays L.) and rice (Oryza sativa L.), which present a suberized exodermis. The analysis herein focused on aliphatic waxes, with particular emphasis on alkyl hydroxycinnamates (AHCs). AHCs were widely distributed, absent from only one species, were found in both aerial and subterranean portions of tuberous taproots, and were associated with the fibrous roots of both maize and rice. Most species also contained monoacylglycerols, fatty alcohols and/or free fatty acids. Carrot (Daucus carrota L.) was the outlier, containing only free fatty acids, sterols, and polyacetylenes as identified components. Sterols were the only ubiquitous component across all roots analyzed. Monoacylglycerols of ω-hydroxy fatty acids were present in maize and rice root waxes. For species within the Brassiceae, wax compositions varied between subspecies or varieties and between aerial and subterranean portions of taproots. In addition, reduced forms of photo-oxidation products of ω-hydroxy oleate and its corresponding dicarboxylic acid (10,18-dihydroxy-octadec-8-enoate, 9,18-dihydroxy-octadec-10-enoate and 9-hydroxyoctadec-10-ene-1,18-dioate) were identified as naturally occurring suberin monomers in rutabaga (Brassica napus subsp. rapifera Metzg.) periderm tissues. PMID:26143051

  15. Safety in the Chemical Laboratory: Nitric Acid, Nitrates, and Nitro Compounds.

    ERIC Educational Resources Information Center

    Bretherick, Leslie

    1989-01-01

    Discussed are the potential hazards associated with nitric acid, inorganic and organic nitrate salts, alkyl nitrates, acyl nitrates, aliphatic nitro compounds, aromatic nitro compounds, and nitration reactions. (CW)

  16. Competitive Oxidation and Reduction of Aliphatic Alcohols over (WO3)3 Clusters

    SciTech Connect

    Kim, Yu K.; Dohnalek, Zdenek; Kay, Bruce D.; Rousseau, Roger J.

    2009-06-04

    The reactions of C1 to C4 aliphatic alcohols over (WO3)3 clusters were studied experimentally and theoretically using temperature-programmed desorption, infrared reflection-absorption spectroscopy and density functional theory. The results reveal that all C1 to C4 aliphatic alcohols readily react with (WO3)3 clusters by heterolytic cleavage of the RO-H bond to give alkoxy (RO ) bound to W(VI) centers and a proton (H+) attached to the terminal oxygen atom of a tungstyl group (W=O). Two protons adsorbed onto the cluster readily react with the doubly-bonded oxygen to from a water molecule that desorbs at 200-300 K and the alkoxy that undergoes decomposition at higher temperatures into the corresponding alkene, aldehyde, and/or ether. Our theory predicts that all three channels proceed over the W(VI) Lewis acid site with energy barriers of 30-40 kcal/mol, where dehydration is favored over the others. We also present further analysis of the yield and reaction temperature as a function of the alkyl substituents and discuss the origin of the reaction selectivity among the three reaction channels.

  17. Elevated serum triiodothyronine and intellectual and motor disability with paroxysmal dyskinesia caused by a monocarboxylate transporter 8 gene mutation.

    PubMed

    Fuchs, Oliver; Pfarr, Nicole; Pohlenz, Joachim; Schmidt, Heinrich

    2009-03-01

    Monocarboxylate transporter 8 (MCT8 or SLC16A2) is important for the neuronal uptake of triiodothyronine (T3) in its function as a specific and active transporter of thyroid hormones across the cell membrane, thus being essential for human brain development. We report on a German male with Allan-Herndon-Dudley syndrome presenting with severe intellectual and motor disability, paroxysmal dyskinesia combined with truncal muscular hypotonia, and peripheral muscular hypertonia at his current age of 9 years. Additionally, the patient has a lesion in the left putamen region revealed by magnetic resonance imaging and elevated serum T3 levels. The male appeared to have a hemizygous mutation (R271H) in the MCT8 gene that was sequenced directly from genomic DNA and occurred de novo in the maternal germline, as both his mother and his sister were not carriers of the mutation. Ruling out a common polymorphism, 50 normal individuals of the same ethnic background did not harbour the mutation. The identified MCT8 gene mutation (R271H) is very likely to be the genetic cause for neuronal hypothyroidism despite elevated serum T3 levels. PMID:19018842

  18. Distribution of monocarboxylate transporters in the peripheral nervous system suggests putative roles in lactate shuttling and myelination.

    PubMed

    Domènech-Estévez, Enric; Baloui, Hasna; Repond, Cendrine; Rosafio, Katia; Médard, Jean-Jacques; Tricaud, Nicolas; Pellerin, Luc; Chrast, Roman

    2015-03-11

    Lactate, a product of glycolysis, has been shown to play a key role in the metabolic support of neurons/axons in the CNS by both astrocytes and oligodendrocytes through monocarboxylate transporters (MCTs). Despite such importance in the CNS, little is known about MCT expression and lactate function in the PNS. Here we show that mouse MCT1, MCT2, and MCT4 are expressed in the PNS. While DRG neurons express MCT1, myelinating Schwann cells (SCs) coexpress MCT1 and MCT4 in a domain-specific fashion, mainly in regions of noncompact myelin. Interestingly, SC-specific downregulation of MCT1 expression in rat neuron/SC cocultures led to increased myelination, while its downregulation in neurons resulted in a decreased amount of neurofilament. Finally, pure rat SCs grown in the presence of lactate exhibited an increase in the level of expression of the main myelin regulator gene Krox20/Egr2 and the myelin gene P0. These data indicate that lactate homeostasis participates in the regulation of the SC myelination program and reveal that similar to CNS, PNS axon-glial metabolic interactions are most likely mediated by MCTs. PMID:25762662

  19. S-Nitrosation of monocarboxylate transporter 1: inhibition of pyruvate-fueled respiration and proliferation of breast cancer cells.

    PubMed

    Diers, Anne R; Broniowska, Katarzyna A; Chang, Ching-Fang; Hill, R Blake; Hogg, Neil

    2014-04-01

    Energy substrates metabolized through mitochondria (e.g., pyruvate, glutamine) are required for biosynthesis of macromolecules in proliferating cells. Because several mitochondrial proteins are known to be targets of S-nitrosation, we determined whether bioenergetics are modulated by S-nitrosation and defined the subsequent effects on proliferation. The nitrosating agent S-nitroso-L-cysteine (L-CysNO) was used to initiate intracellular S-nitrosation, and treatment decreased mitochondrial function and inhibited proliferation of MCF7 mammary adenocarcinoma cells. Surprisingly, the d-isomer of CysNO (D-CysNO), which is not transported into cells, also caused mitochondrial dysfunction and limited proliferation. Both L- and D-CysNO also inhibited cellular pyruvate uptake and caused S-nitrosation of thiol groups on monocarboxylate transporter 1, a proton-linked pyruvate transporter. These data demonstrate the importance of mitochondrial metabolism in proliferative responses in breast cancer and highlight a novel role for inhibition of metabolic substrate uptake through S-nitrosation of exofacial protein thiols in cellular responses to nitrosative stress.

  20. Lipstick dermatitis due to C18 aliphatic compounds.

    PubMed

    Hayakawa, R; Matsunaga, K; Suzuki, M; Arima, Y; Ohkido, Y

    1987-04-01

    An 18-year-old girl developed cheilitis. She had a past history of lip cream dermatitis, but the cause was not found. Patch tests with 2 lipsticks were strongly positive. Tests with the ingredients were positive to 2 aliphatic compounds, glyceryl diisostearate and diisostearyl malate. Impurities in the materials were suspected as the cause. Analysis by gas chromatography detected 3 chemicals in glyceryl diisostearate and 1 in diisostearyl malate as impurities. Patch testing with the impurities and glyceryl monoisostearate 0.01% pet in glyceryl diisostearate and isostearyl alcohol 0.25% pet in diisostearyl malate were strongly positive. The characteristics common to the 2 chemicals were liquidity at room temperature, branched C18 aliphatic compound and primary alcohol. Chemicals lacking any of the above 3 features did not react.

  1. Determination of aliphatic hydrocarbons in the alga Himanthalia elongata.

    PubMed

    Punín Crespo, M O; Lage Yusty, M A

    2004-02-01

    The algae considered new foods according to Regulation CE 258/97 need a guarantee of their healthfulness before being in the European market. In this work ten samples of the brown alga Himanthalia elongata have been analyzed with the aim of verifying the absence of aliphatic hydrocarbons, due to the ability of the macroalgae to capture lipophilic organic compounds of the marine water coming from accidental or continuous leaks of raw oil and refined products, which happen each year with the growth of the industrialization and the demand of energy. The fat of the samples were Soxhlet extracted using hexane:dichloromethane (1:1) for 7h. The organic fractions were purified using silica microcolumns. The identification and quantification of the aliphatic hydrocarbons have been carried out using gas chromatography (GC) with flame ionization detector (FID). The total hydrocarbon content was between 14.8 and 40.2 microg g(-1) dry weight. PMID:14759670

  2. Biodegradation of Trihalomethanes and Other Halogenated Aliphatic Compounds

    NASA Technical Reports Server (NTRS)

    Smith, G. B.

    1996-01-01

    The biological dehalogenation of common water pollutants such as trichloromethane (chloroform) and other halogenated aliphatic compounds was the subject of this project. Samples from diverse water environments such as from groundwater contaminated with halogenated compounds and wastewaters from regional treatment plants were studied to identify conditions that favor certain dehalogenation reactions over others. Gene probe analyses of DNA extracted from the dichlormethane-degrading wastewater indicated the presence of the gene coding for dichloromethane dehalogenase, indicating the genetic basis for the dechlorination activity observed. These studies indicate that methanogenic bacteria are the organisms responsible for the chloroform dechlorination. Dechlorination of a common chlorofluorocarbon (CFC-11) was identified in samples taken from a regional aquifer contaminated with halogenated aliphatic compounds.

  3. Aliphatics hydrocarbon content in surface sediment from Jakarta Bay, Indonesia

    NASA Astrophysics Data System (ADS)

    YAzis, M.; Asia, L.; Piram, A.; Doumenq, P.; Syakti, A. D.

    2016-02-01

    Sedimentary aliphatic hydrocarbons content have been studied quantitatively and qualitatively using GC/MS method in eight coastal stations located in the Jakarta Bay, North of Jakarta, Indonesia. The total concentrations n-alkanes have ranged from 480 μg.kg-1to 1,935 μg.kg-1sediment dry weight. Several ratios (e.g. CPI24-32, NAR, TAR, Pr/Phy, n-C17/Pr, n- C18/Phyt,n-C29/n-C17, Ʃn-alkanes/n-C16LMW/HMW, Paq and TMD) were used to evaluate the possible sources of terrestrial-marine inputs of these hydrocarbons in the sediments. The various origins of aliphatic hydrocarbons were generally biogenic, including both terrigenous and marine, with an anthropogenic pyrolytic contribution (petrogenic and biogenic combustion). Two stations (G,H) were thehighest concentration and had potential risk to environment

  4. Manganese-Mediated Coupling Reaction of Vinylarenes and Aliphatic Alcohols

    PubMed Central

    Zhang, Wei; Wang, Nai-Xing; Bai, Cui-Bing; Wang, Yan-Jing; Lan, Xing-Wang; Xing, Yalan; Li, Yi-He; Wen, Jia-Long

    2015-01-01

    Alcohols and alkenes are the most abundant and commonly used organic building blocks in the large-scale chemical synthesis. Herein, this is the first time to report a novel and operationally simple coupling reaction of vinylarenes and aliphatic alcohols catalyzed by manganese in the presence of TBHP (tert-butyl hydroperoxide). This coupling reaction provides the oxyalkylated products of vinylarenes with good regioselectivity and accomplishes with the principles of step-economies. A possible reaction mechanism has also been proposed. PMID:26470633

  5. Room Temperature, Metal-Free Arylation of Aliphatic Alcohols

    PubMed Central

    Ghosh, Raju; Lindstedt, Erik; Jalalian, Nazli; Olofsson, Berit

    2014-01-01

    Diaryliodonium salts are demonstrated as efficient arylating agents of aliphatic alcohols under metal-free conditions. The reaction proceeds at room temperature within 90 min to give alkyl aryl ethers in good to excellent yields. Aryl groups with electron-withdrawing substituents are transferred most efficiently, and unsymmetric iodonium salts give chemoselective arylations. The methodology has been applied to the formal synthesis of butoxycaine. PMID:24808991

  6. Aerobic microorganism for the degradation of chlorinated aliphatic hydrocarbons

    DOEpatents

    Fliermans, Carl B.

    1989-01-01

    A chlorinated aliphatic hydrocarbon-degrading microorganism, having American Type Culture Collection accession numbers ATCC 53570 and 53571, in a biologically pure culture aseptically collected from a deep subsurface habitat and enhanced, mineralizes trichloroethylene and tetrachloroethylene to HCl, H.sub.2 O and Co.sub.2 under aerobic conditions stimulated by methane, acetate, methanol, tryptone-yeast extract, propane and propane-methane.

  7. Manganese-Mediated Coupling Reaction of Vinylarenes and Aliphatic Alcohols.

    PubMed

    Zhang, Wei; Wang, Nai-Xing; Bai, Cui-Bing; Wang, Yan-Jing; Lan, Xing-Wang; Xing, Yalan; Li, Yi-He; Wen, Jia-Long

    2015-01-01

    Alcohols and alkenes are the most abundant and commonly used organic building blocks in the large-scale chemical synthesis. Herein, this is the first time to report a novel and operationally simple coupling reaction of vinylarenes and aliphatic alcohols catalyzed by manganese in the presence of TBHP (tert-butyl hydroperoxide). This coupling reaction provides the oxyalkylated products of vinylarenes with good regioselectivity and accomplishes with the principles of step-economies. A possible reaction mechanism has also been proposed. PMID:26470633

  8. Manganese-Mediated Coupling Reaction of Vinylarenes and Aliphatic Alcohols

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Wang, Nai-Xing; Bai, Cui-Bing; Wang, Yan-Jing; Lan, Xing-Wang; Xing, Yalan; Li, Yi-He; Wen, Jia-Long

    2015-10-01

    Alcohols and alkenes are the most abundant and commonly used organic building blocks in the large-scale chemical synthesis. Herein, this is the first time to report a novel and operationally simple coupling reaction of vinylarenes and aliphatic alcohols catalyzed by manganese in the presence of TBHP (tert-butyl hydroperoxide). This coupling reaction provides the oxyalkylated products of vinylarenes with good regioselectivity and accomplishes with the principles of step-economies. A possible reaction mechanism has also been proposed.

  9. Formation and Morphology of "shish-like" Fibril Crystals of Aliphatic Polyesters from the Sheared Melt

    SciTech Connect

    Yamazaki, S.; Itoh, M; Oka, T; Kimura, K

    2010-01-01

    We found the formation of 'shish-like' fibril crystals of aliphatic polyesters such as poly(L-lactic acid) (PLLA), poly({var_epsilon}-caprolactone) (PCL), poly(12-hydroxydodecanoic acid) (PHDA) and poly(16-hydroxyhexadecanoic acid) (PHHA) from the sheared melt with shear rate {gamma} = 5 s{sup -1} observed by polarizing optical microscope (POM). The melting temperature T{sub m}s of obtained fibril crystals of PLLA and PCL were higher than those of spherulites and were close to the equilibrium melting temperature T{sub m}{sup 0}. The small angle X-ray scattering (SAXS) patterns from the bulk sample including fibril crystals, small amount of unoriented small crystals and amorphous showed no peaks arose from the existence of long periods in fibril crystals. These are the evidence that the observed fibril crystals consist of assemblies of a lot of extended chain crystals (ECCs). We observed the morphology of moderately extracted single strand of fibril crystals at the magnification of POM by means of scanning electron microscope. We found that macroscopic fibril crystals of PLLA with diameter d = 10 {micro}m consist of the bundle structure of microscopic fibril crystals with d = 2 {micro}m. From POM observation of the formation of fibril crystals of PLLA and PCL, we showed phase diagrams of molecular weight M and crystallization temperature T{sub c} for the formation of fibril crystals. From these phase diagrams, we evaluated a critical M and T{sub c} for the formation of fibril crystals. Moreover, from the sequential melting and crystallization experiments, it was implied that the entanglement and transesterification play an important role on the formation of fibril crystals of aliphatic polyesters.

  10. Biodegradation of aliphatic vs. aromatic hydrocarbons in fertilized arctic soils

    USGS Publications Warehouse

    Braddock, J.F.

    1999-01-01

    A study was carried out to test a simple bioremediation treatment strategy in the Arctic and analyze the influence of fertilization the degradation of aliphatic and aromatic hydrocarbons, e.g., pristine, n-tetradecane, n-pentadecane, 2-methylnaphthalene, naphthalene, and acenaphthalene. The site was a coarse sand pad that once supported fuel storage tanks. Diesel-range organics concentrations were 250-860 mg/kg soil at the beginning of the study. Replicate field plots treated with fertilizer yielded final concentrations of 0, 50, 100, or 200 mg N/kg soil. Soil pH and soil-water potentials decreased due to fertilizer application. The addition of fertilizer considerably increased soil respiration potentials, but not the populations of microorganisms measured. Fertilizer addition also led to ??? 50% loss of measured aliphatic and aromatic hydrocarbons in surface and subsurface soils. For fertilized plots, hydrocarbon loss was not associated with the quantity of fertilizer added. Losses of aliphatic hydrocarbons were ascribed to biotic processes, while losses of aromatic hydrocarbons were due to biotic and abiotic processes.

  11. Segregation and Alteration of Phenolic and Aliphatic Components of Root and Leaf Litter by Detritivores and Microbes

    NASA Astrophysics Data System (ADS)

    Filley, T. R.; Altmann, J.; Szlavecz, K. A.; Kalbitz, K.; Gamblin, D.; Nierop, K.

    2012-12-01

    The physical and microbial transformation of plant detritus in the litter layer and soil is accompanied by chemical separation of progressively soluble fractions and their movement into the rhizosphere driving subsequent soil processes. We investigated the combined action of specific detritivores, microbial decay, and leaching on the chemical separation of plant aromatic and aliphatic components from root, wood, and leaf tissue using 13C-TMAH thermochemolysis. This method enabled the simultaneous analysis of hydrolyzable tannin and lignin fragments, substituted fatty acids, and condensed tannin composition and revealed process-specific chemical transformations to plant secondary compounds. Long-term incubation and field sampling demonstrated how plant residues are progressively leached of the water soluble, oxidized fragments generated through decay. The residues appeared only slightly altered, in the case of brown rot wood, or enriched in aliphatic fragments, in the case of leaf and root tissue. Water extractable fractions were always selectively dominated by polyphenolics, either as demethylated lignin or tannins, and nearly devoid of aliphatic materials, despite high concentrations in the starting materials. Additionally, for plant materials with high tannin contents, such as pine needles, consumption and passage through some arthropod guts revealed what appeared to be microbially-mediated methylation of phenols, and a loss of tannins in leachates. These findings are indications for an in-situ phenol detoxification mechanism. This research provides important information regarding the links between biochemical decay and the chemical nature of organic matter removed and remaining in the soil profile.

  12. Thermally induced degradation of sulfur-containing aliphatic glucosinolates in broccoli sprouts (Brassica oleracea var. italica) and model systems.

    PubMed

    Hanschen, Franziska S; Platz, Stefanie; Mewis, Inga; Schreiner, Monika; Rohn, Sascha; Kroh, Lothar W

    2012-03-01

    Processing reduces the glucosinolate (GSL) content of plant food, among other aspects due to thermally induced degradation. Since there is little information about the thermal stability of GSL and formation of corresponding breakdown products, the thermally induced degradation of sulfur-containing aliphatic GSL was studied in broccoli sprouts and with isolated GSL in dry medium at different temperatures as well as in aqueous medium at different pH values. Desulfo-GSL have been analyzed with HPLC-DAD, while breakdown products were estimated using GC-FID. Whereas in the broccoli sprouts structural differences of the GSL with regard to thermal stability exist, the various isolated sulfur-containing aliphatic GSL degraded nearly equally and were in general more stable. In broccoli sprouts, methylsulfanylalkyl GSL were more susceptible to degradation at high temperatures, whereas methylsulfinylalkyl GSL were revealed to be more affected in aqueous medium under alkaline conditions. Besides small amounts of isothiocyanates, the main thermally induced breakdown products of sulfur-containing aliphatic GSL were nitriles. Although they were most rapidly formed at comparatively high temperatures under dry heat conditions, their highest concentrations were found after cooking in acidic medium, conditions being typical for domestic processing.

  13. Cost-Benefit Analysis for Alternatives to Aliphatic Isocyanate Polyurethanes

    NASA Technical Reports Server (NTRS)

    Lewis, Pattie

    2007-01-01

    NASA and Air Force Space Command (AFSPC) have similar missions and therefore similar facilities and structures in similar environments. The standard practice for protecting metallic substrates in atmospheric environments is the application of an applied coating system. The most common topcoats used in coating systems are polyurethanes that contain isocyanates. Isocyanates are classified as potential human carcinogens and are known to cause cancer in animals. The primary objective of this effort was to demonstrate and validate alternatives to aliphatic isocyanate polyurethanes resulting in one or more isocyanate-free coatings qualified for use at AFSPC and NASA installations participating in this project. This Cost-Benefit Analysis (CBA) quantifies the estimated capital and process costs of coating alternatives and cost savings relative to the current coatings. The estimates in this CBA are to be used for assessing the relative merits of the selected alternatives. The actual economic effects at any specific facility will depend on the alternative material or technology implemented, the number of actual applications converted, future workloads, and other factors . The participants initially considered eighteen (18) alternative coatings as described in the Potential Alternatives Report entitled Potential Alternatives Report for Validation of Alternatives to Aliphatic Isocyanate Polyurethanes, prepared by ITB. Of those, 8 alternatives were selected for testing in accordance with the Joint Test Protocol entitled Joint Test Protocol for Validation of Alternatives to Aliphatic Isocyanate Polyurethanes, and the Field Test Plan entitled Field Evaluations Test Plan for Validation of Alternatives 10 Aliphatic Isocyanate Polyurethanes, both of which were prepared by ITB. A joint Test Report entitled Joint Test Report for Validation of Alternatives to Aliphatic Isocyanate Polyurethanes, prepared by ITB, documents the results of the laboratory and field testing, as well as any

  14. A rapid and sensitive method for the simultaneous analysis of aliphatic and polar molecules containing free carboxyl groups in plant extracts by LC-MS/MS

    PubMed Central

    2009-01-01

    Background Aliphatic molecules containing free carboxyl groups are important intermediates in many metabolic and signalling reactions, however, they accumulate to low levels in tissues and are not efficiently ionized by electrospray ionization (ESI) compared to more polar substances. Quantification of aliphatic molecules becomes therefore difficult when small amounts of tissue are available for analysis. Traditional methods for analysis of these molecules require purification or enrichment steps, which are onerous when multiple samples need to be analyzed. In contrast to aliphatic molecules, more polar substances containing free carboxyl groups such as some phytohormones are efficiently ionized by ESI and suitable for analysis by LC-MS/MS. Thus, the development of a method with which aliphatic and polar molecules -which their unmodified forms differ dramatically in their efficiencies of ionization by ESI- can be simultaneously detected with similar sensitivities would substantially simplify the analysis of complex biological matrices. Results A simple, rapid, specific and sensitive method for the simultaneous detection and quantification of free aliphatic molecules (e.g., free fatty acids (FFA)) and small polar molecules (e.g., jasmonic acid (JA), salicylic acid (SA)) containing free carboxyl groups by direct derivatization of leaf extracts with Picolinyl reagent followed by LC-MS/MS analysis is presented. The presence of the N atom in the esterified pyridine moiety allowed the efficient ionization of 25 compounds tested irrespective of their chemical structure. The method was validated by comparing the results obtained after analysis of Nicotiana attenuata leaf material with previously described analytical methods. Conclusion The method presented was used to detect 16 compounds in leaf extracts of N. attenuata plants. Importantly, the method can be adapted based on the specific analytes of interest with the only consideration that the molecules must contain at

  15. Novel aliphatic lipid-based diesters for use in lubricant formulations: Structure property investigations

    NASA Astrophysics Data System (ADS)

    Raghunanan, Latchmi Cindy

    Structure-property relationships are increasingly valued for the identification of specifically engineered materials with properties optimized for targeted application(s). In this work, linear and branched diesters for use in lubricant formulations are prepared from lipid-based oleochemicals and their structure-property relationships reported. It is shown that the branched diesters possess exceptional physical property profiles, including suppression of crystallization, and are superior alternatives for use in lubricant formulations. For the linear aliphatic diesters, both high and low temperature properties were predictable functions of total chain length, and both were differently influenced by the fatty acid versus diol chain length. Symmetry did not influence either, although thermal stability decreased and thermal transition temperatures increased with increasing saturation. All of the linear diesters demonstrated Newtonian flow behaviour. Viscosity was also predictable as a function of total chain length; any microstructural features due to structural effects were superseded by mass effects.

  16. Platinum-Catalyzed, Terminal-Selective C(sp(3))-H Oxidation of Aliphatic Amines.

    PubMed

    Lee, Melissa; Sanford, Melanie S

    2015-10-14

    This Communication describes the terminal-selective, Pt-catalyzed C(sp(3))-H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol%. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (iii) it electronically deactivates the C-H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp(3))-H oxidation of a variety of primary, secondary, and tertiary amines. PMID:26439251

  17. Green tea phenolics inhibit butyrate-induced differentiation of colon cancer cells by interacting with monocarboxylate transporter 1.

    PubMed

    Sánchez-Tena, S; Vizán, P; Dudeja, P K; Centelles, J J; Cascante, M

    2013-12-01

    Diet has a significant impact on colorectal cancer and both dietary fiber and plant-derived compounds have been independently shown to be inversely related to colon cancer risk. Butyrate (NaB), one of the principal products of dietary fiber fermentation, induces differentiation of colon cancer cell lines by inhibiting histone deacetylases (HDACs). On the other hand, (-)-epicatechin (EC) and (-)-epigallocatechin gallate (EGCG), two abundant phenolic compounds of green tea, have been shown to exhibit antitumoral properties. In this study we used colon cancer cell lines to study the cellular and molecular events that take place during co-treatment with NaB, EC and EGCG. We found that (i) polyphenols EC and EGCG fail to induce differentiation of colon adenocarcinoma cell lines; (ii) polyphenols EC and EGCG reduce NaB-induced differentiation; (iii) the effect of the polyphenols is specific for NaB, since differentiation induced by other agents, such as trichostatin A (TSA), was unaltered upon EC and EGCG treatment, and (iv) is independent of the HDAC inhibitory activity of NaB. Also, (v) polyphenols partially reduce cellular NaB; and (vi) on a molecular level, reduction of cellular NaB uptake by polyphenols is achieved by impairing the capacity of NaB to relocalize its own transporter (monocarboxylate transporter 1, MCT1) in the plasma membrane. Our findings suggest that beneficial effects of NaB on colorectal cancer may be reduced by green tea phenolic supplementation. This valuable information should be of assistance in choosing a rational design for more effective diet-driven therapeutic interventions in the prevention or treatment of colorectal cancer.

  18. Green tea phenolics inhibit butyrate-induced differentiation of colon cancer cells by interacting with monocarboxylate transporter 1

    PubMed Central

    Sánchez-Tena, S.; Vizán, P.; Dudeja, P.K.; Centelles, J.J.; Cascante, M.

    2016-01-01

    Diet has a significant impact on colorectal cancer and both dietary fiber and plant-derived compounds have been independently shown to be inversely related to colon cancer risk. Butyrate (NaB), one of the principal products of dietary fiber fermentation, induces differentiation of colon cancer cell lines by inhibiting histone deacetylases (HDACs). On the other hand, (−)-epicatechin (EC) and (−)-epigallocatechin gallate (EGCG), two abundant phenolic compounds of green tea, have been shown to exhibit antitumoral properties. In this study we used colon cancer cell lines to study the cellular and molecular events that take place during co-treatment with NaB, EC and EGCG. We found that (i) polyphenols EC and EGCG fail to induce differentiation of colon adenocarcinoma cell lines; (ii) polyphenols EC and EGCG reduce NaB-induced differentiation; (iii) the effect of the polyphenols is specific for NaB, since differentiation induced by other agents, such as trichostatin A (TSA), was unaltered upon EC and EGCG treatment, and (iv) is independent of the HDAC inhibitory activity of NaB. Also, (v) polyphenols partially reduce cellular NaB; and (vi) on a molecular level, reduction of cellular NaB uptake by polyphenols is achieved by impairing the capacity of NaB to relocalize its own transporter (monocarboxylate transporter 1, MCT1) in the plasma membrane. Our findings suggest that beneficial effects of NaB on colorectal cancer may be reduced by green tea phenolic supplementation. This valuable information should be of assistance in choosing a rational design for more effective diet-driven therapeutic interventions in the prevention or treatment of colorectal cancer. PMID:23994611

  19. Deficiency in monocarboxylate transporter 1 (MCT1) in mice delays regeneration of peripheral nerves following sciatic nerve crush.

    PubMed

    Morrison, Brett M; Tsingalia, Akivaga; Vidensky, Svetlana; Lee, Youngjin; Jin, Lin; Farah, Mohamed H; Lengacher, Sylvain; Magistretti, Pierre J; Pellerin, Luc; Rothstein, Jeffrey D

    2015-01-01

    Peripheral nerve regeneration following injury occurs spontaneously, but many of the processes require metabolic energy. The mechanism of energy supply to axons has not previously been determined. In the central nervous system, monocarboxylate transporter 1 (MCT1), expressed in oligodendroglia, is critical for supplying lactate or other energy metabolites to axons. In the current study, MCT1 is shown to localize within the peripheral nervous system to perineurial cells, dorsal root ganglion neurons, and Schwann cells by MCT1 immunofluorescence in wild-type mice and tdTomato fluorescence in MCT1 BAC reporter mice. To investigate whether MCT1 is necessary for peripheral nerve regeneration, sciatic nerves of MCT1 heterozygous null mice are crushed and peripheral nerve regeneration was quantified electrophysiologically and anatomically. Compound muscle action potential (CMAP) recovery is delayed from a median of 21 days in wild-type mice to greater than 38 days in MCT1 heterozygote null mice. In fact, half of the MCT1 heterozygote null mice have no recovery of CMAP at 42 days, while all of the wild-type mice recovered. In addition, muscle fibers remain 40% more atrophic and neuromuscular junctions 40% more denervated at 42 days post-crush in the MCT1 heterozygote null mice than wild-type mice. The delay in nerve regeneration is not only in motor axons, as the number of regenerated axons in the sural sensory nerve of MCT1 heterozygote null mice at 4 weeks and tibial mixed sensory and motor nerve at 3 weeks is also significantly reduced compared to wild-type mice. This delay in regeneration may be partly due to failed Schwann cell function, as there is reduced early phagocytosis of myelin debris and remyelination of axon segments. These data for the first time demonstrate that MCT1 is critical for regeneration of both sensory and motor axons in mice following sciatic nerve crush. PMID:25447940

  20. Assessing the Origins of Aliphatic Amines in the Murchison Meteorite from their Compound-Specific Carbon Isotopic Ratios and Enantiomeric Composition

    NASA Technical Reports Server (NTRS)

    Aponte, Jose; Dworkin, Jason; Elsila, Jamie E.

    2014-01-01

    The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of L-enantiomeric excesses for alpha-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are chemically related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with delta C-13 values ranging from +21% to +129%, showing a decrease in C-13 with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an L-enantiomeric excess of 9.7; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential

  1. Assessing the origins of aliphatic amines in the Murchison meteorite from their compound-specific carbon isotopic ratios and enantiomeric composition

    NASA Astrophysics Data System (ADS)

    Aponte, José C.; Dworkin, Jason P.; Elsila, Jamie E.

    2014-09-01

    The study of meteoritic organic compounds provides a unique window into the chemical inventory of the early Solar System and prebiotic chemistry that may have been important for the origin of life on Earth. Multiple families of organic compounds have been extracted from the Murchison meteorite, which is one of the most thoroughly studied carbonaceous chondrites. The amino acids extracted from Murchison have been extensively analyzed, including measurements of non-terrestrial stable isotopic ratios and discoveries of L-enantiomeric excesses for α-dialkyl amino acids, notably isovaline. However, although the isotopic signatures of bulk amine-containing fractions have been measured, the isotopic ratios and enantiomeric composition of individual aliphatic amines, compounds that are structurally related to amino acids, remain unknown. Here, we report a novel method for the extraction, separation, identification and quantitation of aliphatic monoamines extracted from the Murchison meteorite. Our results show a complete suite of structural isomers, with a larger concentration of methylamine and ethylamine and decreasing amine concentrations with increasing carbon number. The carbon isotopic compositions of fourteen meteoritic aliphatic monoamines were measured, with δ13C values ranging from +21‰ to +129‰, showing a decrease in 13C with increasing carbon number, a relationship that may be consistent with the chain elongation mechanism under kinetic control previously proposed for meteoritic amino acids. We also found the enantiomeric composition of sec-butylamine, a structural analog to isovaline, was racemic within error, while the isovaline extracted from the same Murchison piece showed an L-enantiomeric excess of 9.7%; this result suggested that processes leading to enantiomeric excess in the amino acid did not affect the amine. We used these collective data to assess the primordial synthetic origins of these meteoritic aliphatic amines and their potential linkage

  2. Aliphatic peptidyl hydroperoxides as a source of secondary oxidation in hydroxyl radical protein footprinting

    PubMed Central

    Saladino, Jessica; Liu, Mian; Live, David; Sharp, Joshua S.

    2009-01-01

    Hydroxyl radical footprinting is a technique for studying protein structure and binding that entails oxidizing a protein system of interest with diffusing hydroxyl radicals, and then measuring the amount of oxidation of each amino acid. One important issue in hydroxyl radical footprinting is limiting amino acid oxidation by secondary oxidants to prevent uncontrolled oxidation which can cause amino acids to appear more solvent accessible than they really are. Previous work suggested that hydrogen peroxide was the major secondary oxidant of concern in hydroxyl radical footprinting experiments; however, even after elimination of all hydrogen peroxide, some secondary oxidation was still detected. Evidence is presented for the formation of peptidyl hydroperoxides as the most abundant product upon oxidation of aliphatic amino acids. Both reverse phase liquid chromatography and catalase treatment were shown to be ineffective at eliminating peptidyl hydroperoxides. The ability of these peptidyl hydroperoxides to directly oxidize methionine is demonstrated, suggesting the value of methionine amide as an in situ protectant. Hydroxyl radical footprinting protocols require the use of an organic sulfide or similar peroxide scavenger in addition to removal of hydrogen peroxide in order to successfully eradicate all secondary oxidizing species and prevent uncontrolled oxidation of sulfur-containing residues. PMID:19278868

  3. Aliphatic polyesters: great degradable polymers that cannot do everything.

    PubMed

    Vert, Michel

    2005-01-01

    Nowadays the open and the patent literatures propose a large number of polymers whose main chains can be degraded usefully. Among these degradable polymers, aliphatic polyester-based polymeric structures are receiving special attention because they are all more or less sensitive to hydrolytic degradation, a feature of interest when compared with the fact that living systems function in aqueous media. Only some of these aliphatic polyesters are enzymatically degradable. A smaller number is biodegradable, and an even more limited number is biorecyclable. To be of practical interest, a degradable polymer must fulfill many requirements that depend very much on the targeted application, on the considered living system, and on living conditions. It is shown that aliphatic polyester structures made of repeating units that can generate metabolites upon degradation or biodegradation like poly(beta-hydroxy alkanoate)s and poly(alpha-hydroxy alkanoate)s are of special interest. Their main characteristics are confronted to the specifications required by various potential sectors of applications, namely, surgery, pharmacology, and the environment. It is shown that degradation, bioresorption, and biorecycling that are targets when one wants to respect living systems are also drastic limiting factors when one wants to achieve a device of practical interest. Finding a universal polymer that would be the source of all the polymeric biomaterials needed to work in contact with living organisms of the various life kingdoms and respect them remains a dream. On the other hand, finding one polymeric structure than can fulfill the requirements of one niche application remains a big issue.

  4. Aliphatic Polyethers: Classical Polymers for the 21st Century.

    PubMed

    Klein, Rebecca; Wurm, Frederik R

    2015-06-01

    Polyethers-polymers with the structural element (R'-O-R)n in their backbone--are an old class of polymers which were already used at the time of the ancient Egyptians. However, still today these materials are highly important with applications in all areas of our life, reaching from the automotive and paper industry to cosmetics and biomedical applications. In this Review, different aliphatic polyethers like poly(epoxide)s, poly(oxetane)s, and poly(tetrahydrofuran) are discussed. Special emphasis is placed on the history, the polymerization techniques (industrially and in academia), the properties, the applications as well as recent developments of these materials.

  5. Manganese-catalyzed selective oxidation of aliphatic C-H groups and secondary alcohols to ketones with hydrogen peroxide.

    PubMed

    Dong, Jia Jia; Unjaroen, Duenpen; Mecozzi, Francesco; Harvey, Emma C; Saisaha, Pattama; Pijper, Dirk; de Boer, Johannes W; Alsters, Paul; Feringa, Ben L; Browne, Wesley R

    2013-09-01

    An efficient and simple method for selective oxidation of secondary alcohols and oxidation of alkanes to ketones is reported. An in situ prepared catalyst is employed based on manganese(II) salts, pyridine-2-carboxylic acid, and butanedione, which provides good-to-excellent conversions and yields with high turnover numbers (up to 10 000) with H2 O2 as oxidant at ambient temperatures. In substrates bearing multiple alcohol groups, secondary alcohols are converted to ketones selectively and, in general, benzyl C-H oxidation proceeds in preference to aliphatic C-H oxidation.

  6. Palladium-catalyzed hydroaminocarbonylation of alkenes with amines: a strategy to overcome the basicity barrier imparted by aliphatic amines.

    PubMed

    Zhang, Guoying; Gao, Bao; Huang, Hanmin

    2015-06-22

    A novel and efficient palladium-catalyzed hydroaminocarbonylation of alkenes with aminals has been developed under mild reaction conditions, and allows the synthesis of a wide range of N-alkyl linear amides in good yields with high regioselectivity. On the basis of this method, a cooperative catalytic system operating by the synergistic combination of palladium, paraformaldehyde, and acid was established for promoting the hydroaminocarbonylation of alkenes with both aromatic and aliphatic amines, which do not react well under conventional palladium-catalyzed hydroaminocarbonylation.

  7. Terrestrial ecotoxicity of short aliphatic protic ionic liquids.

    PubMed

    Peric, Brezana; Martí, Esther; Sierra, Jordi; Cruañas, Robert; Iglesias, Miguel; Garau, Maria Antonia

    2011-12-01

    A study of the ecotoxicity of different short aliphatic protic ionic liquids (PILs) on terrestrial organisms was conducted. Tests performed within the present study include those assessing the effects of PILs on soil microbial functions (carbon and nitrogen mineralization) and terrestrial plants. The results show that the nominal lowest-observed-adverse-effect concentration (LOAEC) values were 5,000 mg/kg (dry soil) for the plant test in two species (Lolium perenne, Allium cepa), 1,000 mg/kg (dry soil) for the plant test in one species (Raphanus sativus), and 10,000 mg/kg (dry soil) for carbon and nitrogen microbial transformation tests (all concentrations are nominal). Most of the median effective concentration values (EC50) were above 1,000 mg/kg (dry soil). Based on the obtained results, these compounds can be described as nontoxic for soil microbiota and the analyzed plants, and potentially biodegradable in soils, as can be deduced from the respirometric experiment. The toxicity rises with the increase of complexity of the PILs molecule (branch and length of aliphatic chain) among the three PILs analyzed. PMID:21935980

  8. Effects of aliphatic aldehydes on the growth and patulin production of Penicillium expansum in apple juice.

    PubMed

    Taguchi, Tomoyasu; Kozutsumi, Daisuke; Nakamura, Ruka; Sato, Yoshio; Ishihara, Atsushi; Nakajima, Hiromitsu

    2013-01-01

    The effects of 16 aliphatic aldehydes with 3-10 carbons on the growth and patulin production of Penicillium expansum were examined. When P. expansum spores were inoculated into apple juice broth, some alkenals, including 2-propenal, (E)-2-butenal, (E)-2-pentenal, and (E)-2-hexenal, inhibited fungal growth and patulin production. Their minimal inhibitory concentrations were 5, 50, 80, and 80 µg/mL respectively. Vital staining indicated that these alkenals killed mycelia within 4 h. Treatment of the spores with these aldehydes also resulted in rapid loss of germination ability, within 0.5-2 d. On the other hand, aliphatic aldehydes with 8-10 carbons significantly enhanced patulin production without affecting fungal growth: 300 µg/mL of octanal and 100 µg/mL of (E)-2-octenal increased the patulin concentrations in the culture broth by as much as 8.6- and 7.8-fold as compared to that of the control culture respectively. The expression of the genes involved in patulin biosynthesis in P. expansum was investigated in mycelia cultured in apple juice broth containing 300 µg/mL of octanal for 3.5, 5, and 7 d. Transcription of the msas gene, encoding 6-methylsalicylic acid synthase, which catalyzed the first step in the patulin biosynthetic pathway was remarkably high in the 3.5-d and 5-d-old cultures as compared with the control. However, octanal did not any increase the transcription of the msas in the 7-d-old culture or that of the other two genes, IDH and the peab1, in culture. Thus the enhanced patulin accumulation with supplementation with these aldehydes is attributable to the increased amount of the msas transcript.

  9. Aliphatic and eudesmalolide esters extracted from the roots of Inula racemosa Hook

    PubMed Central

    Khan, Maria; Mir, S.R.; Ali, Abuzar; Yusuf, Mohammad; Ali, Mohammed

    2014-01-01

    Background: Phytochemical investigation of hydroalcoholic extract of the root of Inula racemosa Hook. Materials and Methods: Open silica gel column chromatographic techniques with different solvent systems was used for isolation of aliphatic and eudesmalolide esters from hydroalcoholic extract of the root of Inula racemosa. The structure elucidation of the compounds was done on the basis of spectral data analysis, chemical reactions and comparision with literature data. Results: Phytochemical investigation of the hydroalcoholic extract of the root of Inula racemosa Hook. f. led to the isolation of (5z, 13z)-n-decanyl-n-docos-5, 13-dienoate, a new fatty acid ester, two new sesquiterpenic ester identified as 15-[(13z, 18′z, 20′z)-n-tricos-13, 18, 20-trienyl]-eudesmal-4 (11), 6, 12 (13)-trien-8,14-olide-15-oate and 15- [(16′z), (21′z)-n- tetracos-16′, 21′- dienyl]-eudesmal-4 (11) 6, 12 (13)-trien-8, 14-olide-15-oate, two new eudesmanolide ester i.e. 15-[(16z)-n-monadec-16′- enyl]-eudesmal-4 (11) 6, 12 (13)-trien-8,14-olide-15-oate and 15-[(16′z)-n-tetracos-16′- enyl]-endesmal-4 (11), 6, 12 (13)-trien-8,14-olide-15-oate along with the known compound n-Hexadecanyl n-docosanoate. Conclusion: Five new phytoconstituents were identified along with one known compound as aliphatic and eudesmalolide esters from the hydroalcoholic extract of the root of Inula racemosa, as mentioned above. PMID:24695458

  10. Clickable degradable aliphatic polyesters via copolymerization with alkyne epoxy esters: synthesis and postfunctionalization with organic dyes.

    PubMed

    Teske, Nele S; Voigt, Julia; Shastri, V Prasad

    2014-07-23

    Degradable aliphatic polyesters are the cornerstones of nanoparticle (NP)-based therapeutics. In this paradigm, covalent modification of the NP with cell-targeting motifs and dyes can aid in guiding the NP to its destination and gaining visual confirmation. Therefore, strategies to impart chemistries along the polymer backbone that are amenable to easy modification, such as 1,3-dipolar cycloaddition of an azide to an alkyne (the "click reaction"), could be significant. Here we present a simple and efficient way to introduce alkyne groups at high density in aliphatic polyesters without compromising their crystallinity via the copolymerization of cyclic lactones with propargyl 3-methylpentenoate oxide (PMPO). Copolymers of lactic acid and ε-caprolactone with PMPO were synthesized with up to 9 mol % alkyne content, and accessibility of the alkyne groups to the click reaction was demonstrated using several dyes commonly employed in fluorescence microscopy and imaging (Cy3, ATTO-740, and coumarin 343). In order to establish the suitability of these copolymers as nanocarriers, copolymers were formulated into NPs, and cytocompatibility, cellular uptake, and visualization studies undertaken in HeLa cells. Dye-modified NPs exhibited no quenching, remained stable in solution for at least 10 days, showed no cytotoxicity, and were readily taken up by HeLa cells. Furthermore, in addition to enabling the incorporation of multiple fluorophores within the same NP through blending of individual dye-modified copolymers, dye-modified polyesters offer advantages over physical entrapment of dye, including improved signal to noise ratio and localization of the fluorescence signal within cells, and possess the necessary prerequisites for drug delivery and imaging.

  11. Sulfoxide-TFAA and nucleophile combination as new reagent for aliphatic C-H functionalization at indole 2α-position.

    PubMed

    Tayu, Masanori; Higuchi, Kazuhiro; Inaba, Masato; Kawasaki, Tomomi

    2013-01-21

    Aliphatic C-H functionalization at indole 2α-position mediated by acyloxythionium species 1 generated from sulfoxide and acid anhydride has been developed. The combination of sulfoxide and TFAA with O-, N- and C-nucleophiles enabled introduction of various substituents in a one-pot procedure. Especially on utilizing DMSO, the combination provided a practical and efficient method for the synthesis of a wide range of 2α-substituted indoles.

  12. Two Novel Flavin-Containing Monooxygenases Involved in Biosynthesis of Aliphatic Glucosinolates.

    PubMed

    Kong, Wenwen; Li, Jing; Yu, Qingyue; Cang, Wei; Xu, Rui; Wang, Yang; Ji, Wei

    2016-01-01

    Glucosinolates, a class of secondary metabolites from cruciferous plants, are derived from amino acids and have diverse biological activities, such as in biotic defense, depending on their side chain modification. The first structural modification step in the synthesis of aliphatic (methionine-derived) glucosinolates-S-oxygenation of methylthioalkyl glucosinolates to methylsulfinylalkyl glucosinolates-was found to be catalyzed by five flavin-containing monooxygenases (FMOs), FMOGS-OX1-5. Here, we report two additional FMOGS-OX enzymes, FMOGS-OX6, and FMOGS-OX7, encoded by At1g12130 and At1g12160, respectively. The overexpression of both FMOGS-OX6 and FMOGS-OX7 decreased the ratio of methylthioalkyl glucosinolates to the sum of methylthioalkyl and methylsulfinylalkyl glucosinolates, suggesting that the introduction of the two genes converted methylthioalkyl glucosinolates into methylsulfinylalkyl glucosinolates. Analysis of expression pattern revealed that the spatial expression of the two genes is quite similar and partially overlapped with the other FMOGS-OX genes, which are primarily expressed in vascular tissue. We further analyzed the responsive expression pattern of all the seven FMOGS-OX genes to exogenous treatment with abscisic acid, 1-aminocyclopropane-1-carboxylic acid (ACC), jasmonic acid (JA), salicylic acid, indole-3-acetic acid (IAA), and low and high temperatures. Although these genes showed same tendency toward the changing stimulus, the sensitivity of each gene was quite different. The variety in spatial expression among the FMOGS-OX genes while responding to environmental stimulus indicated a complex and finely tuned regulation of glucosinolates modifications. Identification of these two novel FMOGS-OX enzymes will enhance the understanding of glucosinolates modifications and the importance of evolution of these duplicated genes. PMID:27621741

  13. Two Novel Flavin-Containing Monooxygenases Involved in Biosynthesis of Aliphatic Glucosinolates

    PubMed Central

    Kong, Wenwen; Li, Jing; Yu, Qingyue; Cang, Wei; Xu, Rui; Wang, Yang; Ji, Wei

    2016-01-01

    Glucosinolates, a class of secondary metabolites from cruciferous plants, are derived from amino acids and have diverse biological activities, such as in biotic defense, depending on their side chain modification. The first structural modification step in the synthesis of aliphatic (methionine-derived) glucosinolates—S-oxygenation of methylthioalkyl glucosinolates to methylsulfinylalkyl glucosinolates—was found to be catalyzed by five flavin-containing monooxygenases (FMOs), FMOGS-OX1-5. Here, we report two additional FMOGS-OX enzymes, FMOGS-OX6, and FMOGS-OX7, encoded by At1g12130 and At1g12160, respectively. The overexpression of both FMOGS-OX6 and FMOGS-OX7 decreased the ratio of methylthioalkyl glucosinolates to the sum of methylthioalkyl and methylsulfinylalkyl glucosinolates, suggesting that the introduction of the two genes converted methylthioalkyl glucosinolates into methylsulfinylalkyl glucosinolates. Analysis of expression pattern revealed that the spatial expression of the two genes is quite similar and partially overlapped with the other FMOGS-OX genes, which are primarily expressed in vascular tissue. We further analyzed the responsive expression pattern of all the seven FMOGS-OX genes to exogenous treatment with abscisic acid, 1-aminocyclopropane-1-carboxylic acid (ACC), jasmonic acid (JA), salicylic acid, indole-3-acetic acid (IAA), and low and high temperatures. Although these genes showed same tendency toward the changing stimulus, the sensitivity of each gene was quite different. The variety in spatial expression among the FMOGS-OX genes while responding to environmental stimulus indicated a complex and finely tuned regulation of glucosinolates modifications. Identification of these two novel FMOGS-OX enzymes will enhance the understanding of glucosinolates modifications and the importance of evolution of these duplicated genes.

  14. Two Novel Flavin-Containing Monooxygenases Involved in Biosynthesis of Aliphatic Glucosinolates

    PubMed Central

    Kong, Wenwen; Li, Jing; Yu, Qingyue; Cang, Wei; Xu, Rui; Wang, Yang; Ji, Wei

    2016-01-01

    Glucosinolates, a class of secondary metabolites from cruciferous plants, are derived from amino acids and have diverse biological activities, such as in biotic defense, depending on their side chain modification. The first structural modification step in the synthesis of aliphatic (methionine-derived) glucosinolates—S-oxygenation of methylthioalkyl glucosinolates to methylsulfinylalkyl glucosinolates—was found to be catalyzed by five flavin-containing monooxygenases (FMOs), FMOGS-OX1-5. Here, we report two additional FMOGS-OX enzymes, FMOGS-OX6, and FMOGS-OX7, encoded by At1g12130 and At1g12160, respectively. The overexpression of both FMOGS-OX6 and FMOGS-OX7 decreased the ratio of methylthioalkyl glucosinolates to the sum of methylthioalkyl and methylsulfinylalkyl glucosinolates, suggesting that the introduction of the two genes converted methylthioalkyl glucosinolates into methylsulfinylalkyl glucosinolates. Analysis of expression pattern revealed that the spatial expression of the two genes is quite similar and partially overlapped with the other FMOGS-OX genes, which are primarily expressed in vascular tissue. We further analyzed the responsive expression pattern of all the seven FMOGS-OX genes to exogenous treatment with abscisic acid, 1-aminocyclopropane-1-carboxylic acid (ACC), jasmonic acid (JA), salicylic acid, indole-3-acetic acid (IAA), and low and high temperatures. Although these genes showed same tendency toward the changing stimulus, the sensitivity of each gene was quite different. The variety in spatial expression among the FMOGS-OX genes while responding to environmental stimulus indicated a complex and finely tuned regulation of glucosinolates modifications. Identification of these two novel FMOGS-OX enzymes will enhance the understanding of glucosinolates modifications and the importance of evolution of these duplicated genes. PMID:27621741

  15. 40 CFR 721.10605 - Polyoxyalkylene ether, polymer with aliphatic diisocyanate, homopolymer, alkanol-blocked (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polyoxyalkylene ether, polymer with..., polymer with aliphatic diisocyanate, homopolymer, alkanol-blocked (generic). (a) Chemical substance and... polyoxyalkylene ether, polymer with aliphatic diisocyanate, homopolymer, alkanol-blocked (PMN P-11-485) is...

  16. 40 CFR 721.10605 - Polyoxyalkylene ether, polymer with aliphatic diisocyanate, homopolymer, alkanol-blocked (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Polyoxyalkylene ether, polymer with..., polymer with aliphatic diisocyanate, homopolymer, alkanol-blocked (generic). (a) Chemical substance and... polyoxyalkylene ether, polymer with aliphatic diisocyanate, homopolymer, alkanol-blocked (PMN P-11-485) is...

  17. 40 CFR 721.7250 - Polyaziridinyl ester of an aliphatic alcohol (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... alcohol (generic). 721.7250 Section 721.7250 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.7250 Polyaziridinyl ester of an aliphatic alcohol (generic). (a... generically as a polyaziridinyl ester of an aliphatic alcohol (PMN P-01-97) is subject to reporting under...

  18. 40 CFR 721.7250 - Polyaziridinyl ester of an aliphatic alcohol (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... alcohol (generic). 721.7250 Section 721.7250 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.7250 Polyaziridinyl ester of an aliphatic alcohol (generic). (a... generically as a polyaziridinyl ester of an aliphatic alcohol (PMN P-01-97) is subject to reporting under...

  19. 40 CFR 721.7250 - Polyaziridinyl ester of an aliphatic alcohol (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... alcohol (generic). 721.7250 Section 721.7250 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.7250 Polyaziridinyl ester of an aliphatic alcohol (generic). (a... generically as a polyaziridinyl ester of an aliphatic alcohol (PMN P-01-97) is subject to reporting under...

  20. 40 CFR 721.7250 - Polyaziridinyl ester of an aliphatic alcohol (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... alcohol (generic). 721.7250 Section 721.7250 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.7250 Polyaziridinyl ester of an aliphatic alcohol (generic). (a... generically as a polyaziridinyl ester of an aliphatic alcohol (PMN P-01-97) is subject to reporting under...

  1. 40 CFR 721.9952 - Alkoxylated aliphatic diisocyanate allyl ether (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... allyl ether (generic). 721.9952 Section 721.9952 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.9952 Alkoxylated aliphatic diisocyanate allyl ether... identified generically as alkoxylated aliphatic diisocyanate allyl ether (PMN P-00-0353) is subject...

  2. 40 CFR 721.9952 - Alkoxylated aliphatic diisocyanate allyl ether (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... allyl ether (generic). 721.9952 Section 721.9952 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.9952 Alkoxylated aliphatic diisocyanate allyl ether... identified generically as alkoxylated aliphatic diisocyanate allyl ether (PMN P-00-0353) is subject...

  3. Preferences in removal of aliphatic and aromatic gasoline components by biofiltration under varied loading.

    PubMed

    Halecky, Martin; Paca, Jan; Kozliak, Evguenii I

    2012-01-01

    Removal of gasoline vapors from waste air was investigated in a bench-scale perlite biofilter for three aromatic-to-aliphatic mass ratios (62/38, 92/8 and 44/56) under different loads, varied by changing both the substrate inlet concentration and air flow rate. The measurement of concentration profiles along the bed height allowed for an assessment of interactions between the aromatic and aliphatic fractions of gasoline. Variations in both the inlet concentrations and empty bed residence time significantly influenced the removal of aliphatic gasoline components. Except for the lowest organic loads, the whole biofilter bed was required for achieving an acceptable removal efficiency of aliphatic hydrocarbons. The presence of large amounts of aromatics negatively impacted the removal of aliphatics. By contrast, the aromatic gasoline components were near-completely removed from any mixtures; the bulk of them were degraded in the first (out of three) biofilter section, even at high concentrations of aliphatic hydrocarbons. The observed effect was shown to be due to competitive interactions of aliphatic and aromatic components, which is consistent with the biological steps being rate limiting. Mass transfer, particularly for aliphatic components due to their high Henry's law constants, was shown to be rate-limiting under extreme scenarios, such as low loading rates and EBRT.

  4. A statistical approach to the interpretation of aliphatic hydrocarbon distributions in marine sediments

    USGS Publications Warehouse

    Rapp, J.B.

    1991-01-01

    Q-mode factor analysis was used to quantitate the distribution of the major aliphatic hydrocarbon (n-alkanes, pristane, phytane) systems in sediments from a variety of marine environments. The compositions of the pure end members of the systems were obtained from factor scores and the distribution of the systems within each sample was obtained from factor loadings. All the data, from the diverse environments sampled (estuarine (San Francisco Bay), fresh-water (San Francisco Peninsula), polar-marine (Antarctica) and geothermal-marine (Gorda Ridge) sediments), were reduced to three major systems: a terrestrial system (mostly high molecular weight aliphatics with odd-numbered-carbon predominance), a mature system (mostly low molecular weight aliphatics without predominance) and a system containing mostly high molecular weight aliphatics with even-numbered-carbon predominance. With this statistical approach, it is possible to assign the percentage contribution from various sources to the observed distribution of aliphatic hydrocarbons in each sediment sample. ?? 1991.

  5. Surface Characterization of Aliphatic Polyester -g- Phosphorylcholine Copolymers

    NASA Astrophysics Data System (ADS)

    Zhang, Xiongfei; Emrick, Todd; Hsu, Shaw L.

    2007-03-01

    In order to control biodegradation behavior of a class of polyesters, hydrophilic functional groups were grafted onto the main chains. Phosphorylcholine (PC) molecules with azide attached at the end were synthesized. Due to their excellent biocompatibility and hydrophilicity, they have been covalently coupled to biodegradable aliphatic polyesters via a ``click'' cycloaddition reaction to produce amphiphilic graft copolymers. A series of copolymers were prepared by varying the molar incorporation of PC groups. Surface properties of the copolymers were examined to further explore their applications in drug delivery systems. Grazing angle reflection infrared spectroscopy was employed to determine segmental orientation at the film surface. XPS was used to verify surface composition. A water adsorption experiment was carried out to determine the water permeation rate. The improvement in hydrophilicity was confirmed by a water contact experiment. Results indicate that the graft copolymers were promising in drug delivery systems.

  6. The Role of Monocarboxylate Transporters and Their Chaperone CD147 in Lactate Efflux Inhibition and the Anticancer Effects of Terminalia chebula in Neuroblastoma Cell Line N2-A

    PubMed Central

    Messeha, S. S.; Zarmouh, N. O.; Taka, E.; Gendy, S. G.; Shokry, G. R.; Kolta, M. G.; Soliman, K. F. A.

    2016-01-01

    Aims In the presence of oxygen, most of the synthesized pyruvate during glycolysis in the cancer cell of solid tumors is released away from the mitochondria to form lactate (Warburg Effect). To maintain cell homeostasis, lactate is transported across the cell membrane by monocarboxylate transporters (MCTs). The major aim of the current investigation is to identify novel compounds that inhibit lactate efflux that may lead to identifying effective targets for cancer treatment. Study Design In this study, 900 ethanol plant extracts were screened for their lactate efflux inhibition using neuroblastoma (N2-A) cell line. Additionally, we investigated the mechanism of inhibition for the most potent plant extract regarding monocarboxylate transporters expression, and consequences effects on viability, growth, and apoptosis. Methodology The potency of lactate efflux inhibition of ethanol plant extracts was evaluated in N2-A cells by measuring extracellular lactate levels. Caspase 3- activity and acridine orange/ethidium bromide staining were performed to assess the apoptotic effect. The antiproliferative effect was measured using WST assay. Western blotting was performed to quantify protein expression of MCTs and their chaperone CD147 in treated cells lysates. Results Terminalia chebula plant extract was the most potent lactate efflux inhibitor in N2-A cells among the 900 - tested plant extracts. The results obtained show that extract of Terminalia chebula fruits (TCE) significantly (P = 0.05) reduced the expression of the MCT1, MCT3, MCT4 and the chaperone CD147. The plant extract was more potent (IC50 of 3.59 ± 0.26 μg/ml) than the MCT standard inhibitor phloretin (IC50 76.54 ± 3.19 μg/ml). The extract also showed more potency and selective cytotoxicity in cancer cells than DI-TNC1 primary cell line (IC50 7.37 ± 0.28 vs. 17.35 ± 0.19 μg/ml). Moreover, TCE Inhibited N2-A cell growth (IG50 = 5.20 ± 0.30 μg/ml) and induced apoptosis at the 7.5 μg/ml concentration

  7. Enantiomeric effects on excitation-contraction coupling in frog skeletal muscle by a chiral phenoxy carboxylic acid.

    PubMed Central

    Heiny, J A; Jong, D; Bryant, S H; Conte-Camerino, D; Tortorella, V

    1990-01-01

    Aromatic monocarboxylic acids are known to significantly potentiate the mechanical response of skeletal muscle fibers. In this study we investigated the effects of enantiomers of 2-(4-chlorophenoxy)propionic acid, chemically one of the simplest aromatic monocarboxylic acids with chiral properties, on mechanical threshold and charge movement in frog skeletal muscle. The R(+), but not the S(-), enantiomer lowered rheobase mechanical threshold and shifted charge movement to more negative potentials. The R(+) enantiomer also significantly slowed charge movement kinetics, with pronounced delays of the OFF charge transitions. These effects required high temperature for their production. The stereospecific actions of the R(+) enantiomer are interpreted in terms of a specific interaction of this compound at an anion-sensitive site involved in excitation-contraction coupling, most likely on the dihydropryidine-sensitive voltage sensor in the T-system. PMID:2297560

  8. Gene Expression of Monocarboxylate Transporters and Oocyte-secreted Factors in Bovine Cumulus-oocyte Complexes Selected by Brilliant Cresyl Blue.

    PubMed

    Lopes, E F; Marques, L S; Duranti, R G; de Oliveira, A T D; Lopes, R F F; Rodrigues, J L

    2015-10-01

    Oocyte selection based on the brilliant cresyl blue (BCB) staining test has been successfully used to differentiate between competent and incompetent bovine oocytes. Here, the expression of genes involved in transport of monocarboxylates (Mct1-4) and oogenesis specific genes (Bmp15, Gdf9 and Has2) in BCB+ and BCB- selected immature and mature bovine cumulus-oocyte complexes (COC) was evaluated. In order to find specific molecular markers to characterize successful oocyte maturation, our study was also aimed at identifying the expression of Mcts and oogenesis specific genes in denuded oocytes and cumulus cells. Immature COCs morphological appropriate were (i) stained with 26 mm BCB for 90 min before IVM, (ii) exposed to same incubation conditions as stained COCs, but without BCB (holding group) or (iii) transferred into a maturation medium immediately after morphological selection (control group). mRNA expression was investigated by RT-PCR in COCs before and after IVM. No relationship was observed in the relative expression of Has2, Gdf9, Bmp15 or Mct1, 2 and 4 transcripts between BCB+ and BCB- COCs. Transcripts analysis showed that Gdf9 and Bmp15 in BCB+, BCB- and holding groups were up-regulated (p < 0.05) before IVM, while Has2 was up-regulated (p < 0.01) after IVM in the control group. Other genes remained stable during maturation (Mct1, 2 and 4). Our results showed, for the first time, Mct1, 2 and 4 expression in bovine COCs. Mct1 and Mct4 transcripts were present in denuded oocytes and cumulus cell, while Mct2 was detected only in cumulus cells. These differences between the three isoforms in localization suggest unique roles for each in monocarboxylate transport during maturation.

  9. [A novel nano-hydroxyapatite/aliphatic polyesteramide composite].

    PubMed

    Deng, Xia; Chen, Zhiqing; Qian, Zhiyong; Liu, Caibing; Li, Hong

    2008-04-01

    Hydrothermally synthesized nano-hydroxyapatite (n-HA) varying in weight from 10% to 30% was used as filler to make nanocomposites with novel aliphatic polyesteramide (PEA) in our laboratory. The structure and properties of PEA and its n-HA composites were investigated through transmission electron microscopy, infrared spectrometry, X-ray diffractioin, scanning electron microscopy and energy spectrometry. The shape and size of the n-HA crystals are similar to those of the apatite crystals in natural bone. Molecule interactions are present between the n-HA and PEA in the composite, which allows the uniform dispersion of n-HA in PEA matrix. This contributes enhanced mechanical property and bioactivity to the composite. The cytocompatibility of the composites has been investigated by culturing osteoblasts on the membranes. Good cell attachment and proliferation manner were observed on the membranes after 1 week. These results suggest that the PEA/n-HA composites prepared in this study may serve as potential candidate scaffold for tissue engineering.

  10. Liquid-crystalline aromatic-aliphatic copolyester bioresorbable polymers.

    PubMed

    de Oca, Horacio Montes; Wilson, Joanne E; Penrose, Andrew; Langton, David M; Dagger, Anthony C; Anderson, Melissa; Farrar, David F; Lovell, Christopher S; Ries, Michael E; Ward, Ian M; Wilson, Andrew D; Cowling, Stephen J; Saez, Isabel M; Goodby, John W

    2010-10-01

    The synthesis and characterisation of a series of liquid-crystalline aromatic-aliphatic copolyesters are presented. Differential scanning calorimetry showed these polymers have a glass transition temperature in the range 72 degrees C-116 degrees C. Polarised optical microscopy showed each polymer exhibits a nematic mesophase on heating to the molten state at temperatures below 165 degrees C. Melt processing is demonstrated by the production of injection moulded and compression moulded specimens with Young's modulus of 5.7 +/- 0.3 GPa and 2.3 +/- 0.3 GPa, respectively. Wide-angle X-ray scattering data showed molecular orientation is responsible for the increase of mechanical properties along the injection direction. Degradation studies in the temperature range 37 degrees C-80 degrees C are presented for one polymer of this series and a kinetic constant of 0.002 days(-1) is obtained at 37 degrees C assuming a first order reaction. The activation energy (83.4 kJ mol(-1)) is obtained following the Arrhenius analysis of degradation, showing degradation of this material is less temperature sensitive compared with other commercially available biodegradable polyesters. In vitro and in vivo biocompatibility data are presented and it is shown the unique combination of degradative, mechanical and biological properties of these polymers may represent in the future an alternative for medical device manufacturers.

  11. Organochlorine compounds and aliphatic hydrocarbons in Pacific walrus blubber.

    PubMed

    Seagars, D J; Garlich-Miller, J

    2001-01-01

    Blubber samples were collected from 8 male and 19 female Pacific walrus (Odobenus rosmarus divergens) taken during a 1991 joint USA/USSR cruise traveling widely through the Bering Sea. Dieldrin was found at a level similar to that reported 10 years earlier; oxychlordane was found at a slightly higher concentration than reported previously (Taylor et aL, 1989). Heptachlor epoxide was detected for the first time and found at a low concentration. An initial testing for alpha-, beta- and gamma-HCH detected concentrations similar to those in other Bering Sea pinnipeds. Mean summation of PCB was 0.45 microg g(-1) wet weight in males and 0.16 microg g(-1) in females; only one sample was > 1 microg g(-1). Traces of aliphatic hydrocarbons were detected in all sampled animals, only pristane (x = 0.48 microg g(-1)) was found in concentrations > 1 microg g(-1). Small sample sizes, a lack of samples from immature animals, and uniformly low concentrations of contaminants precluded meaningful analysis of age-related effects and regional differences.

  12. Aliphatic polyesters for medical imaging and theranostic applications.

    PubMed

    Nottelet, Benjamin; Darcos, Vincent; Coudane, Jean

    2015-11-01

    Medical imaging is a cornerstone of modern medicine. In that context the development of innovative imaging systems combining biomaterials and contrast agents (CAs)/imaging probes (IPs) for improved diagnostic and theranostic applications focuses intense research efforts. In particular, the classical aliphatic (co)polyesters poly(lactide) (PLA), poly(lactide-co-glycolide) (PLGA) and poly(ɛ-caprolactone) (PCL), attract much attention due to their long track record in the medical field. This review aims therefore at providing a state-of-the-art of polyester-based imaging systems. In a first section a rapid description of the various imaging modalities, including magnetic resonance imaging (MRI), optical imaging, computed tomography (CT), ultrasound (US) and radionuclide imaging (SPECT, PET) will be given. Then, the two main strategies used to combine the CAs/IPs and the polyesters will be discussed. In more detail we will first present the strategies relying on CAs/IPs encapsulation in nanoparticles, micelles, dendrimers or capsules. We will then present chemical modifications of polyesters backbones and/or polyester surfaces to yield macromolecular imaging agents. Finally, opportunities offered by these innovative systems will be illustrated with some recent examples in the fields of cell labeling, diagnostic or theranostic applications and medical devices.

  13. Process for the synthesis of aliphatic alcohol-containing mixtures

    DOEpatents

    Greene, M.I.; Gelbein, A.P.

    1984-10-16

    A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200 to 450 C and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

  14. Process for the synthesis of aliphatic alcohol-containing mixtures

    DOEpatents

    Greene, Marvin I.; Gelbein, Abraham P.

    1984-01-01

    A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200.degree. to 450.degree. C. and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

  15. Shape memory polymers based on uniform aliphatic urethane networks

    SciTech Connect

    Wilson, T S; Bearinger, J P; Herberg, J L; Marion III, J E; Wright, W J; Evans, C L; Maitland, D J

    2007-01-19

    Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, in order to form amorphous networks with very uniform supermolecular structures which can be used as photo-thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N{prime},N{prime}-tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3-butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34 to 153 C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T{sub g}. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices.

  16. Electrospun aliphatic polycarbonates as tailored tissue scaffold materials.

    PubMed

    Welle, Alexander; Kröger, Mario; Döring, Manfred; Niederer, Kerstin; Pindel, Elvira; Chronakis, Ioannis S

    2007-04-01

    Two different aliphatic polycarbonates were synthesised from CO(2) and the respective epoxides. Poly(propyl carbonate) (PPC) was prepared by heterogeneous catalysis with zinc glutarate. Poly(cyclohexyl carbonate) (PCHC) was prepared via living copolymerisation homogeneously catalysed by a 3-amino-2-cyanoimidoacrylate zinc acetate complex and subjected to electrospinning. The obtained nanofibres had a well-defined morphology free of beads along the fibres and with slightly porous structures on their surface. Subsequently, low-power deep UV irradiations, previously applied for photochemical surface modifications of two-dimensional and three-dimensional scaffolds from biostable polymers, were performed. Here, an effect on surface and bulk properties of PPC nanofibres was observed. Surface modifications of both polymers affected plasma protein adsorption. Photochemical bulk modifications observed for the first time on PPC nanofibres are indicating the possibility of spatial control of biodegradation rates, hence allow for control of the progression of host/implant interactions in vivo. In particular PPC was used for cell culture of L929 fibroblasts and primary rat hepatocytes. Even delicate primary cells showed good adhesion to the scaffolds and high viability.

  17. Aliphatic hydrocarbons in Great Barrier Reef organisms and environment

    NASA Astrophysics Data System (ADS)

    Coates, M.; Connell, D. W.; Bodero, J.; Miller, G. J.; Back, R.

    1986-07-01

    This investigation was undertaken to assess the chemical nature, occurrence, and possible origin of petroleum hydrocarbons in the Great Barrier Reef ecosystem. Aliphatic hydrocarbons in surface sediments, water, and a suite of seven species from widely separated coral reefs in the Great Barrier Reef area were analysed by gas chromatography, and by gas chromatography coupled with mass spectrometry. The hydrocarbons found were substantially of biogenic origin. The major components were n-pentadecane, n-heptadecane, pristane and mono-alkenes based on heptadecane, and were believed to originate from benthic algae and phytoplankton. There was no evidence to suggest that lipid content had any influence on hydrocarbon content. Hydrocarbons from the organisms and sediments have characteristic composition patterns which would be altered by the presence of petroleum hydrocarbons. An unresolved complex mixture, usually considered indicative of petroleum contamination, was found in greater than trace amounts only in Holothuria (sea cucumber) and Acropora (coral) from the Capricorn Group, and in some sediment samples from the Capricorn Group and Lizard Island area.

  18. Synthesis and characterization of water-soluble chitosan grafted with hydrophilic aliphatic polyester.

    PubMed

    Chen, Jiajia; Zheng, Liuchun; Chen, Xiaonong; Wang, Zhaodong; Li, Chuncheng; Xiao, Yaonan; Guan, Guohu; Zhu, Wenxiang

    2015-03-01

    Traditionally, hydrophobic aliphatic polyester has been employed to modify chitosan and organic soluble or swellable graft copolymers have been obtained. In this work, linear poly(butylene tartrate) (PBT) with hydrophilic pendant hydroxyl groups, which was synthesized by direct polycondensation of tartaric acid and butanediol under mild condition, was chosen to modify chitosan and synthesize PBT grafted chitosan (CS-g-PBT) with the mediation of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide in aqueous solution of an ionic liquid. The chain length of the grafted PBT could be facilely controlled by varying the molecular weight of PBT. The chemical structures of CS-g-PBT were systematically characterized by 1H NMR, attenuated total reflectance Fourier transform infrared and wide-angle X-ray diffraction. The thermal properties were investigated by thermogravimetric analysis and differential scanning calorimetry. The water solubility of chitosan has been effectively improved after grafting with PBT and a water-soluble chitosan derivative has been synthesized. Meanwhile, the water solubility of grafts varies regularly with chain length of grafted PBT. PMID:25576746

  19. Aliphatic hyperbranched polyester: a new building block in the construction of multifunctional nanoparticles and nanocomposites.

    PubMed

    Santra, Santimukul; Kaittanis, Charalambos; Perez, J Manuel

    2010-04-20

    Herein we report the design and synthesis of multifunctional hyperbranched polyester-based nanoparticles and nanocomposites with properties ranging from magnetic, fluorescence, antioxidant and X-ray contrast. The fabrication of these nanostructures was achieved using a novel aliphatic and biodegradable hyperbranched polyester (HBPE) synthesized from readily available diethyl malonate. The polymer's globular structure with functional surface carboxylic groups and hydrophobic cavities residing in the polymer's interior allows for the formation of multifunctional polymeric nanoparticles, which are able to encapsulate a diversity of hydrophobic cargos. Via simple surface chemistry modifications, the surface carboxylic acid groups were modified to yield nanoparticles with a variety of surface functionalizations, such as amino, azide and propargyl groups, which mediated the conjugation of small molecules. This capability achieved the engineering of the HBPE nanoparticle surface for specific cell internalization studies and the formation of nanoparticle assemblies for the creation of novel nanocomposites that retained, and in some cases enhanced, the properties of the parental nanoparticle building blocks. Considering these results, the HBPE polymer, nanoparticles and composites should be ideal for biomedical, pharmaceutical, nanophotonics applications. PMID:19957939

  20. Divergent layer topologies in divalent metal aliphatic dicarboxylate coordination polymers containing 3-pyridylmethylnicotinamide

    NASA Astrophysics Data System (ADS)

    White, Charmaine L.; Torres Salgado, Maria D.; Mizzi, Jessica E.; LaDuca, Robert L.

    2015-12-01

    Hydrothermal reaction of the requisite metal salt, an aliphatic dicarboxylic acid, and the hydrogen-bonding capable dipyridylamide ligand 3-pyridylmethylnicotinamide (3-pmna) resulted in four coordination polymers whose connectedness and layer topology depend on the metal coordination environment and dicarboxylate binding mode. These new crystalline phases were characterized by single crystal X-ray diffraction. [Cu(ox)(3-pmna)]n (1, ox = oxalate) manifests stacked 3-connected (6,3) herringbone layer motifs. {[Cd(mal)(3-pmna)(H2O)]·3H2O}n (2, mal = malonate) shows a 4-connected (4,4) grid topology with entrained water molecule trimeric chains in the interlamellar regions. {[Cd2(suc)2(3-pmna)(H2O)2]·3H2O}n (3, suc = succinate) possesses {Cd2O2} dimer-based [Cd(suc)]n layers pillared by 3-pmna ligands into a 5-connected sandwich motif with 4862 topology. {[Cd(glu)(3-pmna)(H2O)]·3H2O}n (4, glu = glutarate) manifests a rippled (4,4) grid topology. Luminescent behavior in the cadmium complexes is ascribed to intra-ligand molecular orbital transitions. Thermal decomposition behavior is also discussed herein.

  1. Different aliphatic dicarboxylates affected assemble of new coordination polymers constructed from flexible-rigid mixed ligands

    SciTech Connect

    Xu Xinxin; Ma Ying; Wang Enbo

    2007-11-15

    In this article, seven coordination polymers: [Cd(C{sub 5}H{sub 6}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})]{sub n} (1), [Zn(C{sub 5}H{sub 6}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})]{sub n} (2), [Cd(C{sub 6}H{sub 8}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})]{sub n} (3), {l_brace}[Mn(C{sub 10}H{sub 8}N{sub 2})(H{sub 2}O){sub 4}] (C{sub 4}H{sub 4}O{sub 4}).4H{sub 2}O{r_brace}{sub n} (4), [Mn{sub 5}(C{sub 4}H{sub 4}O{sub 4}){sub 4}(O)]{sub n} (5), [Cd(C{sub 4}H{sub 4}O{sub 4})(C{sub 10}H{sub 8}N{sub 2})(H{sub 2}O)]{sub n} (6) and [Zn(C{sub 6}H{sub 6}O{sub 4})(C{sub 12}H{sub 8}N{sub 2})(H{sub 2}O)]{sub n} (7) were synthesized and characterized by single-crystallographic X-ray diffraction. Compounds 1 and 2 are two-dimensional layers connected by glutarate anions and 4,4'-bpy. Unlike compounds 1 and 2, compound 3 is a two-fold interpenetration network. Compound 4 is a one-dimensional chain-like structure, which is further extended to two-dimensional supramolecular layer structure with hydrogen bond. During the synthesis of compound 4, to our surprise, we got compound 5; compound 5 is an interesting three-dimensional network composed of pentanuclear Mn(II) building units and succinate anions. Compound 6 is also a two-dimensional supramolecular layer structure composed of one-dimensional chain-like structure with hydrogen bonds and {pi}-{pi} interactions. Compound 7 is also a one-dimensional chain-like structure, which is further connected with the same kind of interaction to generate two-dimensional supramolecular layer structure. Furthermore, compounds 1 and 2 both exhibit fluorescent property at room temperature. - Graphical abstract: Seven complexes composed by 3D metal ions, aliphatic acid ligand and rigid bidentate nitrogen ligands: 4,4'-bpy, 2,2'-bpy and 1,10'-phen. With the change of the carbon number of the backbone of aliphatic dicarboxylate ligand, we can synthesize different complexes with various structures.

  2. Project Summary. IN-SITU AQUIFER RESTORATION OF CHLORINATED ALIPHATICS BY METHANOTROPHIC BACTERIA

    EPA Science Inventory

    This project evaluated the potential of an innovative approach to aquifer restoration: enhanced in-situ biotransformation of chlorinated aliphatic solvents by a bacterial community grown on methane under aerobic conditions. The target chlorinated compounds were trichloroethene (...

  3. Field Evaluations Test Plan for Validation of Alternatives to Aliphatic Isocyanate Polyurethanes

    NASA Technical Reports Server (NTRS)

    Lewis, Pattie

    2005-01-01

    The objective of this project is to qualify candidate alternatives to Aliphatic Isocyanate Polyurethane coatings under the specifications for the standard system. This project will compare coating performance of the proposed alternatives to existing coating systems or standards.

  4. Radiation induced effects in segmented poly(siloxaneurethaneureas) based on aliphatic and aromatic diisocyanates

    NASA Astrophysics Data System (ADS)

    Przybytniak, Grażyna; Kornacka, Ewa; Kozakiewicz, Janusz; Przybylski, Jarosław

    2007-12-01

    Poly(siloxaneurethaneureas) (PSURURs) prepared from aromatic and aliphatic isocyanates were investigated upon exposure to ionising radiation. Radicals are formed both in siloxane and urethane segments. In comparison with aliphatic analogues it was found that in aromatic PSURURs: (1) concentration of all radicals is lower, (2) relative concentration of methylene radicals formed in siloxane units is higher, (3) the radiation yield of H 2 is more than three times smaller and (4) it seems that efficiency of cross-linking is less significant.

  5. Recent Advances in the Functionalization of Aliphatic Polyesters by Ring-Opening Polymerization

    NASA Astrophysics Data System (ADS)

    Lecomte, Philippe; Jerome, Christine

    Two main strategies aiming at synthesizing aliphatic polyesters bearing pendant functional groups will be reported. The first one is based on the synthesis and the polymerization of lactones substituted by various functional groups. The direct grafting of functional groups onto aliphatic polyesters is the second strategy. Last but not least, the association of these two strategies is very promising in order to overcome their respective limitations.

  6. Sources and distribution of aliphatic and polyaromatic hydrocarbons in sediments from the Neuquen River, Argentine Patagonia.

    PubMed

    Monza, Liliana B; Loewy, Ruth M; Savini, Mónica C; Pechen de d'Angelo, Ana M

    2013-01-01

    Spatial distribution and probable sources of aliphatic and polyaromatic hydrocarbons (AHs, PAHs) were investigated in surface sediments collected along the bank of the Neuquen River, Argentina. Total concentrations of aliphatic hydrocarbons ranged between 0.41 and 125 μg/g dw. Six stations presented low values of resolved aliphatic hydrocarbons and the n-alkane distribution indexes applied suggested a clear biogenic source. These values can be considered the baseline levels of aliphatic hydrocarbons for the river sediments. This constitutes important information for the assessment of future impacts since a strong impulse in the exploitation of shale gas and shale oil in these zones is nowadays undergoing. For the other 11 stations, a mixture of aliphatic hydrocarbons of petrogenic and biogenic origin was observed. The spatial distribution reflects local inputs of these pollutants with a significant increase in concentrations in the lower course, where two major cities are located. The highest values of total aliphatic hydrocarbons were found in this sector which, in turn, was the only one where individual PAHs were detected.

  7. THE CARRIERS OF THE INTERSTELLAR UNIDENTIFIED INFRARED EMISSION FEATURES: AROMATIC OR ALIPHATIC?

    SciTech Connect

    Li Aigen; Draine, B. T. E-mail: draine@astro.princeton.edu

    2012-12-01

    The unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 {mu}m, commonly attributed to polycyclic aromatic hydrocarbon (PAH) molecules, have been recently ascribed to coal- or kerogen-like organic nanoparticles with a mixed aromatic-aliphatic structure. However, we show in this Letter that this hypothesis is inconsistent with observations. We estimate the aliphatic fraction of the UIE carriers based on the observed intensities of the 3.4 {mu}m and 6.85 {mu}m emission features by attributing them exclusively to aliphatic C-H stretch and aliphatic C-H deformation vibrational modes, respectively. We derive the fraction of carbon atoms in aliphatic form to be <15%. We conclude that the UIE emitters are predominantly aromatic, with aliphatic material at most a minor part of the UIE carriers. The PAH model is consistent with astronomical observations and PAHs dominate the strong UIE bands.

  8. A note on the prebiotic synthesis of organic acids in carbonaceous meteorites

    NASA Technical Reports Server (NTRS)

    Kerridge, John F.

    1991-01-01

    Strong similarities between monocarboxylic and hydrocarboxylic acids in the Murchison meteorite suggest corresponding similarities in their origins. However, various lines of evidence apparently implicate quite different precursor compounds in the synthesis of the different acids. These seeming inconsistencies can be resolved by postulating that the apparent precursors also share a related origin. Pervasive D enrichment indicates that this origin was in a presolar molecular cloud. The organic acids themselves were probably synthesized in an aqueous environment on an asteroidal parent body, the hydroxy (and amino) acids by means of the Strecker cyanohydrin reaction.

  9. Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite.

    PubMed

    Epstein, S; Krishnamurthy, R V; Cronin, J R; Pizzarello, S; Yuen, G U

    1987-04-01

    Much effort has been directed to analyses of organic compounds in carbonaceous chondrites because of their implications for organic chemical evolution and the origin of life. We have determined the isotopic composition of hydrogen, nitrogen and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite. The unusually high D/H and 15N/14N ratios in the amino acid fraction (delta D = 1,370% after correction for isotope exchange; delta 15N = 90) are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower (377%), but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound, and provide the first evidence suggesting a direct relationship between the massive organo-synthesis occurring in interstellar clouds and the presence of pre-biotic compounds in primitive planetary bodies. The isotope data also bear on the historical problem of distinguishing indigenous material from terrestrial contaminants.

  10. Aliphatic polyester block polymers: renewable, degradable, and sustainable.

    PubMed

    Hillmyer, Marc A; Tolman, William B

    2014-08-19

    Nearly all polymers are derived from nonrenewable fossil resources, and their disposal at their end of use presents significant environmental problems. Nonetheless, polymers are ubiquitous, key components in myriad technologies and are simply indispensible for modern society. An important overarching goal in contemporary polymer research is to develop sustainable alternatives to "petro-polymers" that have competitive performance properties and price, are derived from renewable resources, and may be easily and safely recycled or degraded. Aliphatic polyesters are particularly attractive targets that may be prepared in highly controlled fashion by ring-opening polymerization of bioderived lactones. However, property profiles of polyesters derived from single monomers (homopolymers) can limit their applications, thus demanding alternative strategies. One such strategy is to link distinct polymeric segments in an A-B-A fashion, with A and B chosen to be thermodynamically incompatible so that they can self-organize on a nanometer-length scale and adopt morphologies that endow them with tunable properties. For example, such triblock copolymers can be useful as thermoplastic elastomers, in pressure sensitive adhesive formulations, and as toughening modifiers. Inspired by the tremendous utility of petroleum-derived styrenic triblock copolymers, we aimed to develop syntheses and understand the structure-property profiles of sustainable alternatives, focusing on all renewable and all readily degradable aliphatic polyester triblocks as targets. Building upon oxidation chemistry reported more than a century ago, a constituent of the peppermint plant, (-)-menthol, was converted to the ε-caprolactone derivative menthide. Using a diol initiator and controlled catalysis, menthide was polymerized to yield a low glass transition temperature telechelic polymer (PM) that was then further functionalized using the biomass-derived monomer lactide (LA) to yield fully renewable PLA

  11. Aliphatic polyester block polymers: renewable, degradable, and sustainable.

    PubMed

    Hillmyer, Marc A; Tolman, William B

    2014-08-19

    Nearly all polymers are derived from nonrenewable fossil resources, and their disposal at their end of use presents significant environmental problems. Nonetheless, polymers are ubiquitous, key components in myriad technologies and are simply indispensible for modern society. An important overarching goal in contemporary polymer research is to develop sustainable alternatives to "petro-polymers" that have competitive performance properties and price, are derived from renewable resources, and may be easily and safely recycled or degraded. Aliphatic polyesters are particularly attractive targets that may be prepared in highly controlled fashion by ring-opening polymerization of bioderived lactones. However, property profiles of polyesters derived from single monomers (homopolymers) can limit their applications, thus demanding alternative strategies. One such strategy is to link distinct polymeric segments in an A-B-A fashion, with A and B chosen to be thermodynamically incompatible so that they can self-organize on a nanometer-length scale and adopt morphologies that endow them with tunable properties. For example, such triblock copolymers can be useful as thermoplastic elastomers, in pressure sensitive adhesive formulations, and as toughening modifiers. Inspired by the tremendous utility of petroleum-derived styrenic triblock copolymers, we aimed to develop syntheses and understand the structure-property profiles of sustainable alternatives, focusing on all renewable and all readily degradable aliphatic polyester triblocks as targets. Building upon oxidation chemistry reported more than a century ago, a constituent of the peppermint plant, (-)-menthol, was converted to the ε-caprolactone derivative menthide. Using a diol initiator and controlled catalysis, menthide was polymerized to yield a low glass transition temperature telechelic polymer (PM) that was then further functionalized using the biomass-derived monomer lactide (LA) to yield fully renewable PLA

  12. Interaction of gaseous aromatic and aliphatic compounds in thermophilic biofilters.

    PubMed

    Hu, Qing-yuan; Wang, Can

    2015-12-30

    Two thermophilic biofilters were applied in treating a mixture of gaseous aromatic (benzene) and aliphatic compounds (hexane) to evaluate the interaction of the compounds. The performance of the biofilters was investigated in terms of removal efficiencies, elimination capacity, kinetic analysis, interaction indices, and microbial metabolic characteristics. Results showed that the removal performance of benzene was unaffected by the addition of hexane. The removal efficiencies of benzene were maintained at approximately 80% and the biodegradation rate constant was maintained at 120 h(-1). However, the removal efficiencies of hexane decreased significantly from 60% to 20% and the biodegradation rate constant exhibited a distinct decrease from 93.59 h(-1) to 56.32 h(-1). The interaction index of benzene with the addition of hexane was -0.029, which indicated that hexane had little effect on the degradation of benzene. By contrast, the interaction index of hexane by benzene was -0.557, which showed that benzene inhibited the degradation of hexane significantly. Similar conclusions were obtained about the substrate utilization. Moreover, the utilization degree of carbon sources and the microbial metabolic activities in the biofilter treating hexane were significantly improved with the addition of benzene, whereas the addition of hexane had a slight effect on the microbial communities in the biofilter treating benzene. Conclusions could be obtained that when mixtures of benzene and hexane were treated using biofilters, the degradation of benzene, which was more easily degradable, was dominant and unaffected; whereas the degradation of hexane, which was less easily degradable, was inhibited because of the changing of microbes.

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

    PubMed

    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. Physicochemical and ion-binding properties of highly aliphatic humic substances extracted from deep sedimentary groundwater.

    PubMed

    Saito, Takumi; Terashima, Motoki; Aoyagi, Noboru; Nagao, Seiya; Fujitake, Nobuhide; Ohnuki, Toshihiko

    2015-08-01

    Humic substances (HSs) are ubiquitous in various aquatic systems and play important roles in many geochemical processes. There is increasing evidence of the presence of HSs in deep groundwater; nevertheless, their ion binding properties are largely unknown. In this study we investigated the physicochemical and ion-binding properties of humic and fulvic acids extracted from deep sedimentary groundwater. The binding isotherms of protons (H(+)) and copper (Cu(2+)) were measured by potentiometry and fitted to the NICA-Donnan model, and the obtained parameters were compared with the generic parameters of the model, which are the average parameters for HSs from surface environments. The deep groundwater HSs were different from surface HSs, having high aliphaticities, high sulfur contents, and small molecular sizes. Their amounts of acidic functional groups were comparable to or slightly larger than those of surface HSs; however, the magnitude of Cu(2+) binding to the deep groundwater HSs was smaller. The NICA-Donnan model attributed this to the binding of Cu(2+) to chemically homogeneous low affinity sites, which presumably consist of carboxylic groups, via mono-dentate coordination at relatively low pH. The binding mode tended to shift to multi-dentate coordination with carboxylic groups and more heterogeneous alcoholic/phenolic groups at higher pH. X-ray absorption spectroscopy also revealed that Cu(2+) binds to O/N containing functional groups and to a lesser extent S containing functional groups as its divalent from. This study shows the particularity of the deep groundwater HSs in terms of their physicochemical and ion-binding properties, compared with surface HSs. PMID:26166584

  15. Dicarboxylic acids with limited numbers of hydrocarbons stabilize cell membrane and increase osmotic resistance in rat erythrocytes.

    PubMed

    Mineo, Hitoshi; Amita, Nozomi; Kawawake, Megumi; Higuchi, Ayaka

    2013-11-01

    We examined the effect of dicarboxylic acids having 0 to 6 hydrocarbons and their corresponding monocarboxylic or tricarboxylic acids in changing the osmotic fragility (OF) in rat red blood cells (RBCs). Malonic, succinic, glutaric and adipic acids, which are dicarboxylic acids with 1, 2, 3 and 4 straight hydrocarbons located between two carboxylic groups, decreased the OF in a concentration-dependent manner. Other long-chain dicarboxylic acids did not change the OF in rat RBCs. The benzoic acid derivatives, isophthalic and terephthalic acids, but not phthalic acid, decreased the OF in a concentration-dependent manner. Benzene-1,2,3-tricarboxylic acid, but not benzene-1,3,5-tricarboxylic acid, also decreased the OF in rat RBCs. On the other hand, monocarboxylic acids possessing 2 to 7 straight hydrocarbons and benzoic acid increased the OF in rat RBCs. In short-chain dicarboxylic acids, a limited number of hydrocarbons between the two carboxylic groups are thought to form a V- or U-shaped structure and interact with phospholipids in the RBC membrane. In benzene dicarboxylic and tricarboxylic acids, a part of benzene nucleus between the two carboxylic groups is thought to enter the plasma membrane and act on acyl-chain in phospholipids in the RBC membrane. For dicarboxylic and tricarboxylic acids, limited numbers of hydrocarbons in molecules are speculated to enter the RBC membrane with the hydrophilic carboxylic groups remaining outside, stabilizing the structure of the cell membrane and resulting in an increase in osmotic resistance in rat RBCs.

  16. Aliphatic amines in Antarctic CR2, CM2, and CM1/2 carbonaceous chondrites

    NASA Astrophysics Data System (ADS)

    Aponte, José C.; McLain, Hannah L.; Dworkin, Jason P.; Elsila, Jamie E.

    2016-09-01

    Meteoritic water-soluble organic compounds provide a unique record of the processes that occurred during the formation of the solar system and the chemistry preceding the origins of life on Earth. We have investigated the molecular distribution, compound-specific δ13C isotopic ratios and enantiomeric compositions of aliphatic monoamines present in the hot acid-water extracts of the carbonaceous chondrites LAP 02342 (CR2), GRA 95229 (CR2), LON 94101 (CM2), LEW 90500 (CM2), and ALH 83100 (CM1/2). Analyses of the concentration of monoamines in these meteorites revealed: (a) the CR2 chondrites studied here contain higher concentrations of monoamines relative to the analyzed CM2 chondrites; (b) the concentration of monoamines decreases with increasing carbon number; and (c) isopropylamine is the most abundant monoamine in these CR2 chondrites, while methylamine is the most abundant amine species in these CM2 and CM1/2 chondrites. The δ13C values of monoamines in CR2 chondrite do not correlate with the number of carbon atoms; however, in CM2 and CM1/2 chondrites, the 13C enrichment decreases with increasing monoamine carbon number. The δ13C values of methylamine in CR2 chondrites ranged from -1 to +10‰, while in CM2 and CM1/2 chondrites the δ13C values of methylamine ranged from +41 to +59‰. We also observed racemic compositions of sec-butylamine, 3-methyl-2-butylamine, and sec-pentylamine in the studied carbonaceous chondrites. Additionally, we compared the abundance and δ13C isotopic composition of monoamines to those of their structurally related amino acids. We found that monoamines are less abundant than amino acids in CR2 chondrites, with the opposite being true in CM2 and CM1/2 chondrites. We used these collective data to evaluate different primordial synthetic pathways for monoamines in carbonaceous chondrites and to understand the potential common origins these molecules may share with meteoritic amino acids.

  17. Purification of Pseudomonas putida acyl coenzyme A ligase active with a range of aliphatic and aromatic substrates.

    PubMed Central

    Fernández-Valverde, M; Reglero, A; Martinez-Blanco, H; Luengo, J M

    1993-01-01

    Acyl coenzyme A (acyl-CoA) ligase (acyl-CoA synthetase [ACoAS]) from Pseudomonas putida U was purified to homogeneity (252-fold) after this bacterium was grown in a chemically defined medium containing octanoic acid as the sole carbon source. The enzyme, which has a mass of 67 kDa, showed maximal activity at 40 degrees C in 10 mM K2PO4H-NaPO4H2 buffer (pH 7.0) containing 20% (wt/vol) glycerol. Under these conditions, ACoAS showed hyperbolic behavior against acetate, CoA, and ATP; the Kms calculated for these substrates were 4.0, 0.7, and 5.2 mM, respectively. Acyl-CoA ligase recognizes several aliphatic molecules (acetic, propionic, butyric, valeric, hexanoic, heptanoic, and octanoic acids) as substrates, as well as some aromatic compounds (phenylacetic and phenoxyacetic acids). The broad substrate specificity of ACoAS from P. putida was confirmed by coupling it with acyl-CoA:6-aminopenicillanic acid acyltransferase from Penicillium chrysogenum to study the formation of several penicillins. Images PMID:8476289

  18. Process for removing halogenated aliphatic and aromatic compounds from petroleum products

    DOEpatents

    Googin, John M.; Napier, John M.; Travaglini, Michael A.

    1983-01-01

    A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced.

  19. CZE study on adsorption processes of aliphatic and aromatic amines on PMMA chip.

    PubMed

    Masár, Marián; Kruk, Pavol; Luc, Milan; Bodor, Róbert; Danč, Ladislav; Troška, Peter

    2013-02-01

    Adsorption processes on a PMMA chip linked with CZE separations of a group of 13 aliphatic and aromatic mono- and di-amines were studied. Due to the lack of chromophores within aliphatic amines, contact conductivity detection implemented directly onto the chip was used for monitoring of cationic CZE separations. To prevent an adsorption of studied amines to the chip channels, the surface of PMMA chip was modified by dynamic coating. Different surface modifiers, such as aliphatic oligoamines (diethylenetriamine and triethylenetetramine), were added to the BGE solutions filling the chip channels. The effect of various concentrations of surface modifiers on peak profiles and separation parameters of amines was monitored. Of these, mainly, aliphatic di-amines and aromatic mono-amines adversely affected the CZE resolution of a whole group of analytes by their strong adsorption to the chip channels. A propionate BGE with pH 3.2 containing 100 μM triethylenetetramine and 25 mM 18-crown-6-ether was found suitable for CZE resolution of 12 from a total of 13 amines studied. Simple dynamic modification of the surface of PMMA chip enabled fast (analysis time lasted 9 min), sensitive (sub-μM LODs reached) and reproducible (1-3% RSD of the peak areas) CZE analysis of the aliphatic and aromatic amines.

  20. Process for removing halogenated aliphatic and aromatic compounds from petroleum products

    DOEpatents

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1983-09-20

    A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

  1. Enzymatic Combustion of Aromatic and Aliphatic Compounds by Manganese Peroxidase from Nematoloma frowardii

    PubMed Central

    Hofrichter, Martin; Scheibner, Katrin; Schneegaß, Ivonne; Fritsche, Wolfgang

    1998-01-01

    The direct involvement of manganese peroxidase (MnP) in the mineralization of natural and xenobiotic compounds was evaluated. A broad spectrum of aromatic substances were partially mineralized by the MnP system of the white rot fungus Nematoloma frowardii. The cell-free MnP system partially converted several aromatic compounds, including [U-14C]pentachlorophenol ([U-14C]PCP), [U-14C]catechol, [U-14C]tyrosine, [U-14C]tryptophan, [4,5,9,10-14C]pyrene, and [ring U-14C]2-amino-4,6-dinitrotoluene ([14C]2-AmDNT), to 14CO2. Mineralization was dependent on the ratio of MnP activity to concentration of reduced glutathione (thiol-mediated oxidation), a finding which was demonstrated by using [14C]2-AmDNT as an example. At [14C]2-AmDNT concentrations ranging from 2 to 120 μM, the amount of released 14CO2 was directly proportional to the concentration of [14C]2-AmDNT. The formation of highly polar products was also observed with [14C]2-AmDNT and [U-14C]PCP; these products were probably low-molecular-weight carboxylic acids. Among the aliphatic compounds tested, glyoxalate was mineralized to the greatest extent. Eighty-six percent of the 14COOH-glyoxalate and 9% of the 14CHO-glyoxalate were converted to 14CO2, indicating that decarboxylation reactions may be the final step in MnP-catalyzed mineralization. The extracellular enzymatic combustion catalyzed by MnP could represent an important pathway for the formation of carbon dioxide from recalcitrant xenobiotic compounds and may also have general significance in the overall biodegradation of resistant natural macromolecules, such as lignins and humic substances. PMID:16349496

  2. Development of an environment-friendly microextraction method for the determination of aliphatic and aromatic aldehydes in water.

    PubMed

    Serrano, María; Silva, Manuel; Gallego, Mercedes

    2013-06-19

    Aldehydes are produced in water disinfected primarily by ozone treatment, and are generally present in treated water below the limit of detection (<5 μg L(-1)) of commonly proposed methods. Formaldehyde is the most studied along with acetaldehyde due to their mutagenic character, and because it causes chromosomal aberrations. This paper reports the first miniaturised system for the simultaneous determination of thirteen aldehydes (aliphatic and aromatic) which are selected based on their frequent or suspected presence in water, mainly as disinfection by-products (DBPs). The micro liquid-liquid extraction (MLLE) method is a miniaturisation of EPA Method 556.1 for carbonyl compounds that includes some innovations, such as performing the derivatising reaction in a strong acidic medium (pH 1.1), and the addition of magnesium sulphate to the aqueous layer as the heating agent, which allows to carry out the whole simultaneous derivatisation/microextraction process in only 1 min. Large-volume sample injection (50 μL) coupled to programmed temperature vaporiser-gas chromatography-mass spectrometry is also used to improve both sensitivity and selectivity. The MLLE method demonstrated high extraction efficiency (96%) with low limits of detection, between 0.7 and 80 ng L(-1), and good precision (RSD below 10%, n=11). The proposed method was evaluated by determining aldehydes in water. Our study demonstrated that the selection of the target aldehydes was appropriate since all were found (at average concentrations from 8.0 to 1.4 μg L(-1) for aliphatic and aromatic aldehydes, respectively) in swimming pool waters as DBPs. PMID:23746412

  3. Development of an environment-friendly microextraction method for the determination of aliphatic and aromatic aldehydes in water.

    PubMed

    Serrano, María; Silva, Manuel; Gallego, Mercedes

    2013-06-19

    Aldehydes are produced in water disinfected primarily by ozone treatment, and are generally present in treated water below the limit of detection (<5 μg L(-1)) of commonly proposed methods. Formaldehyde is the most studied along with acetaldehyde due to their mutagenic character, and because it causes chromosomal aberrations. This paper reports the first miniaturised system for the simultaneous determination of thirteen aldehydes (aliphatic and aromatic) which are selected based on their frequent or suspected presence in water, mainly as disinfection by-products (DBPs). The micro liquid-liquid extraction (MLLE) method is a miniaturisation of EPA Method 556.1 for carbonyl compounds that includes some innovations, such as performing the derivatising reaction in a strong acidic medium (pH 1.1), and the addition of magnesium sulphate to the aqueous layer as the heating agent, which allows to carry out the whole simultaneous derivatisation/microextraction process in only 1 min. Large-volume sample injection (50 μL) coupled to programmed temperature vaporiser-gas chromatography-mass spectrometry is also used to improve both sensitivity and selectivity. The MLLE method demonstrated high extraction efficiency (96%) with low limits of detection, between 0.7 and 80 ng L(-1), and good precision (RSD below 10%, n=11). The proposed method was evaluated by determining aldehydes in water. Our study demonstrated that the selection of the target aldehydes was appropriate since all were found (at average concentrations from 8.0 to 1.4 μg L(-1) for aliphatic and aromatic aldehydes, respectively) in swimming pool waters as DBPs.

  4. Anion Effects in Oxidative Aliphatic Carbon-Carbon Bond Cleavage Reactions of Cu(II) Chlorodiketonate Complexes.

    PubMed

    Saraf, Sushma L; Miłaczewska, Anna; Borowski, Tomasz; James, Christopher D; Tierney, David L; Popova, Marina; Arif, Atta M; Berreau, Lisa M

    2016-07-18

    Aliphatic oxidative carbon-carbon bond cleavage reactions involving Cu(II) catalysts and O2 as the terminal oxidant are of significant current interest. However, little is currently known regarding how the nature of the Cu(II) catalyst, including the anions present, influence the reaction with O2. In previous work, we found that exposure of the Cu(II) chlorodiketonate complex [(6-Ph2TPA)Cu(PhC(O)CClC(O)Ph)]ClO4 (1) to O2 results in oxidative aliphatic carbon-carbon bond cleavage within the diketonate unit, leading to the formation of benzoic acid, benzoic anhydride, benzil, and 1,3-diphenylpropanedione as organic products. Kinetic studies of this reaction revealed a slow induction phase followed by a rapid decay of the absorption features of 1. Notably, the induction phase is not present when the reaction is performed in the presence of a catalytic amount of chloride anion. In the studies presented herein, a combination of spectroscopic (UV-vis, EPR) and density functional theory (DFT) methods have been used to examine the chloride and benzoate ion binding properties of 1 under anaerobic conditions. These studies provide evidence that each anion coordinates in an axial position of the Cu(II) center. DFT studies reveal that the presence of the anion in the Cu(II) coordination sphere decreases the barrier for O2 activation and the formation of a Cu(II)-peroxo species. Notably, the chloride anion more effectively lowers the barrier associated with O-O bond cleavage. Thus, the nature of the anion plays an important role in determining the rate of reaction of the diketonate complex with O2. The same type of anion effects were observed in the O2 reactivity of the simple Cu(II)-bipyridine complex [(bpy)Cu(PhC(O)C(Cl)C(O)Ph)ClO4] (3). PMID:27377103

  5. Seasonal distribution of aliphatic hydrocarbons in the Vaza Barris Estuarine System, Sergipe, Brazil.

    PubMed

    Barbosa, José Carlos S; Santos, Lukas G G V; Sant'Anna, Mércia V S; Souza, Michel R R; Damasceno, Flaviana C; Alexandre, Marcelo R

    2016-03-15

    The seasonal assessment of anthropogenic activities in the Vaza Barris estuarine river system, located in the Sergipe state, northeastern Brazil, was performed using the aliphatic hydrocarbon distribution. The aliphatic hydrocarbon and isoprenoid (Pristane and Phytane) concentrations ranged between 0.19 μg g(-1) and 8.5 μg g(-1) of dry weight. Data were analyzed using Kruskal-Wallis test, with significance level set at p<0.05, and no seasonality distribution change was observed. The Carbon Preference Index (CPI), associated with n-alkanes/n-C16, Low Molecular Weight/High Molecular Weight ratio (LMW/HMW) and Terrigenous to Aquatic Ratio (TAR) suggested biogenic input of aliphatic hydrocarbons for most samples, with significant contribution of higher plants.

  6. Aliphatic Hydrocarbons in Surface Sediments of Willapa Bay and Grays Harbor, Washington

    USGS Publications Warehouse

    Rapp, J.B.; Kvenvolden, K.A.; Clifton, H.E.

    1982-01-01

    Willapa Bay and Grays Harbor are two adjacent estuaries along the coast of Washington state. Willapa Bay is a recreational area minimally affected by industry; Grays Harbor, on the other hand, is moderately industrialized. Aliphatic hydrocarbons in surface sediments from these two estuaries reflect the differences in human activities. For example, the mean concentration of aliphatic hydrocarbons for seven stations in Willapa Bay is 1,000 ?g/g (relative to organic carbon) while in Grays Harbor this mean concentration for six stations is 1,900 ?g/g. The difference is attributed mainly to the greater urban and industrial pollution in Grays Harbor. The gas chromatographic records of aliphatic hydrocarbons also reflect the extent of hydrocarbon pollution by the presence of a chromatographically unresolved mixture of hydrocarbons. This kind of mixture is more evident in sediments from Grays Harbor, and in both estuaries it is more concentrated in sediments collected nearest to urban centers.

  7. Effect of glutathione on in vitro metabolism of unsaturated aliphatic nitriles to cyanide

    SciTech Connect

    Farooqui, M.Y.H.; Massa, E. )

    1991-03-01

    Aliphatic nitriles are widely used as important solvents and intermediates in polymer, plastic, synthetic fibers, resins, dyestuffs, pharmaceuticals and vitamin industries. Occupational exposure to these chemicals is principally through inhalation and dermal routes. Human and animal toxicity studies have suggested that the toxicity of aliphatic nitriles is due to their cyanide (CN{sup {minus}}) liberating capacity under biological conditions. Despite the common property of CN{sup {minus}} liberation, their are marked differences among nitriles, in the amounts of CN{sup {minus}} released to cause poisoning, in the duration of exposure and toxicity signs. The extent of metabolism of unsaturated aliphatic nitrile is influenced by the structural properties of the molecule. The purpose of this study is to investigate the effects of functional groups, the type of unsaturated moiety and availability of sulfhydryls especially glutathione (GSH) on the in vitro rat liver postmitochondrial fraction (microsomes + cytosol) is used to provide cytosolic GHS transferase, an essential enzyme of GSH metabolism.

  8. Classical-Reaction-Driven Stereo- and Regioselective C(sp(3) )-H Functionalization of Aliphatic Amines.

    PubMed

    Mahato, Sujit; Jana, Chandan K

    2016-06-01

    A large variety of synthetic methods have been developed for the synthesis of functionalized aliphatic amines because of their broad spectrum of application. Metallic reagents/catalysts and/or toxic oxidants are involved in most of the cases. Direct CH functionalization of aliphatic amines via their classical condensation reactions with suitable carbonyl compounds is advantageous because this method avoids hazardous metallic reagents, toxic oxidants and pre-activation/pre-functionalization step(s). In this account, the concept of direct CH functionalization of aliphatic amines based on the classical condensation-isomerization-addition (CIA) strategy followed by recent contributions from our ongoing research in the field along with relevant examples from other groups are described. Successes in stereo- and regioselective CC and CO bond formation via direct α- as well as β-C(sp(3) )-H functionalization are discussed. PMID:27185195

  9. Extraction of benzene and naphthalene carboxylic acids using quaternary ammonium salts as a model study for the separation of coal oxidation products

    SciTech Connect

    Kawamura, K.; Nagano, H.; Okuwaki, A.

    2005-07-01

    The ion-pair solvent extraction of benzene- and naphthalene-carboxylic acids has been investigated as a model study for the separation of coal oxidation products, which are formed by treatment with alkaline solutions at high temperatures. It was possible that benzene- and naphthalene-dicarboxylic acids are extracted into several types of organic solvents with quaternary ammonium ions. The extraction equilibrium constants (K{sub ex}) for benzoic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 1-naphthoic acid, 2-naphthoic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid into chloroform were determined at 20{sup o}C. The difference of K{sub ex} among the aromatic acids was sufficiently large for designing a separation method for these aromatic acids. It was unexpected that the extraction of dicarboxylic acids was slower than that of monocarboxylic acids, although the ion-pair formation of aromatic carboxylate ion with quaternary ammonium ion is normally considered as a diffusion control reaction in aqueous phase. Thus, this fact suggests that the phase transfer of the ion-pair from aqueous to organic phase is the rate-determining step. Liner-free-energy relationship was observed for the monocarboxylic acids using different quaternary ammonium salts while that was ambiguous for the dicarboxylic acids. This is due to the steric influence of the counter ions for the magnitude of K{sub ex}.

  10. Primordial transport of sugars and amino acids via Schiff bases

    NASA Astrophysics Data System (ADS)

    Stillwell, William; Rau, Aruna

    1981-09-01

    Experimental support is given for a model concerning the origin of a primordial transport system. The model is based on the facilitated diffusion of amino acids stimulated by aliphatic aldehyde carriers and sugars stimulated by aliphatic amine carriers. The lipid-soluble diffusing species is the Schiff base. The possible role of this simple transport system in the origin of an early protocell is discussed.

  11. Friction differences between aliphatic and aromatic structures in lubrication of titanium

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1975-01-01

    Sliding friction experiments were conducted with a titanium (0001) single crystal surface with various adsorbed aliphatic and aromatic compounds containing the same number of carbon atoms. An Auger emission spectroscopy analysis was used to monitor the presence of the organic lubricating compounds. Results of the investigation indicate that hexane and benzene give the same friction coefficients over a range of loads. At light loads the friction decreased with an increase in the halogen atom size where the halogens chlorine, bromine, and iodine are incorporated into the benzene molecular structure. The aliphatic compounds chlorohexane and bromohexane exhibited lower friction coefficients than the aromatic structures chlorobenzene and bromobenzene.

  12. On the aliphatic versus aromatic content of the carriers of the `unidentified' infrared emission features

    NASA Astrophysics Data System (ADS)

    Yang, X. J.; Glaser, R.; Li, Aigen; Zhong, J. X.

    2016-10-01

    Although it is generally accepted that the unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 μm are characteristic of the stretching and bending vibrations of aromatic hydrocarbon materials, the exact nature of their carriers remains unknown: whether they are free-flying, predominantly aromatic gas-phase molecules, or amorphous solids with a mixed aromatic/aliphatic composition are being debated. Recently, the 3.3 and 3.4 μm features which are commonly respectively attributed to aromatic and aliphatic C-H stretches have been used to place an upper limit of ˜2 per cent on the aliphatic fraction of the UIE carriers (i.e. the number of C atoms in aliphatic chains to that in aromatic rings). Here we further explore the aliphatic versus aromatic content of the UIE carriers by examining the ratio of the observed intensity of the 6.2 μm aromatic C-C feature (I6.2) to that of the 6.85 μm aliphatic C-H deformation feature (I6.85). To derive the intrinsic oscillator strengths of the 6.2 μm stretch (A6.2) and the 6.85 μm deformation (A6.85), we employ density functional theory to compute the vibrational spectra of seven methylated polycyclic aromatic hydrocarbon molecules and their cations. By comparing I6.85/I6.2 with A6.85/A6.2, we derive the fraction of C atoms in methyl(ene) aliphatic form to be at most ˜10 per cent, confirming the earlier finding that the UIE emitters are predominantly aromatic. We have also computed the intrinsic strength of the 7.25 μm feature (A7.25), another aliphatic C-H deformation band. We find that A6.85 appreciably exceeds A7.25. This explains why the 6.85 μm feature is more frequently detected in space than the 7.25 μm feature.

  13. ORGANIC CHEMISTRY. Catalytic asymmetric hydroamination of unactivated internal olefins to aliphatic amines.

    PubMed

    Yang, Yang; Shi, Shi-Liang; Niu, Dawen; Liu, Peng; Buchwald, Stephen L

    2015-07-01

    Catalytic assembly of enantiopure aliphatic amines from abundant and readily available precursors has long been recognized as a paramount challenge in synthetic chemistry. Here, we describe a mild and general copper-catalyzed hydroamination that effectively converts unactivated internal olefins—an important yet unexploited class of abundant feedstock chemicals—into highly enantioenriched α-branched amines (≥96% enantiomeric excess) featuring two minimally differentiated aliphatic substituents. This method provides a powerful means to access a broad range of advanced, highly functionalized enantioenriched amines of interest in pharmaceutical research and other areas.

  14. Capillary Electrophoresis Profiles and Fluorophore Components of Humic Acids in Nebraska Corn and Philippine Rice Soils

    Technology Transfer Automated Retrieval System (TEKTRAN)

    As humic substances represent relatively high molecular mass polyelectrolytes containing aromatic, aliphatic and heterocyclic subunits, capillary electrophoresis (CE) has become an attractive method for “finger-print” characterization of humic acids. In addition, fluorescence excitation-emission ma...

  15. 40 CFR 721.10190 - Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... diamine and phenol, reaction products with 4-methyl-2-pentanone (generic). 721.10190 Section 721.10190... Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2-pentanone (generic... identified generically as formaldehyde, polymer with aliphatic diamine and phenol, reaction products with...

  16. 40 CFR 721.10190 - Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... diamine and phenol, reaction products with 4-methyl-2-pentanone (generic). 721.10190 Section 721.10190... Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2-pentanone (generic... identified generically as formaldehyde, polymer with aliphatic diamine and phenol, reaction products with...

  17. 40 CFR 721.10190 - Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... diamine and phenol, reaction products with 4-methyl-2-pentanone (generic). 721.10190 Section 721.10190... Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2-pentanone (generic... identified generically as formaldehyde, polymer with aliphatic diamine and phenol, reaction products with...

  18. 40 CFR 721.10190 - Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... diamine and phenol, reaction products with 4-methyl-2-pentanone (generic). 721.10190 Section 721.10190... Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2-pentanone (generic... identified generically as formaldehyde, polymer with aliphatic diamine and phenol, reaction products with...

  19. 40 CFR 721.10190 - Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... diamine and phenol, reaction products with 4-methyl-2-pentanone (generic). 721.10190 Section 721.10190... Formaldehyde, polymer with aliphatic diamine and phenol, reaction products with 4-methyl-2-pentanone (generic... identified generically as formaldehyde, polymer with aliphatic diamine and phenol, reaction products with...

  20. Process for the extraction of strontium from acidic solutions

    DOEpatents

    Horwitz, E. Philip; Dietz, Mark L.

    1994-01-01

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid.

  1. Process for the extraction of strontium from acidic solutions

    DOEpatents

    Horwitz, E.P.; Dietz, M.L.

    1993-01-01

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid.

  2. Process for the extraction of strontium from acidic solutions

    DOEpatents

    Horwitz, E.P.; Dietz, M.L.

    1994-09-06

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid. 4 figs.

  3. Inhibition of monocarboxylate transporter 2 in the retrotrapezoid nucleus in rats: a test of the astrocyte-neuron lactate-shuttle hypothesis.

    PubMed

    Erlichman, Joseph S; Hewitt, Amy; Damon, Tracey L; Hart, Michael; Kurascz, Jennifer; Li, Aihua; Leiter, James C

    2008-05-01

    The astrocyte-neuronal lactate-shuttle hypothesis posits that lactate released from astrocytes into the extracellular space is metabolized by neurons. The lactate released should alter extracellular pH (pHe), and changes in pH in central chemosensory regions of the brainstem stimulate ventilation. Therefore, we assessed the impact of disrupting the lactate shuttle by administering 100 microM alpha-cyano-4-hydroxy-cinnamate (4-CIN), a dose that blocks the neuronal monocarboxylate transporter (MCT) 2 but not the astrocytic MCTs (MCT1 and MCT4). Administration of 4-CIN focally in the retrotrapezoid nucleus (RTN), a medullary central chemosensory nucleus, increased ventilation and decreased pHe in intact animals. In medullary brain slices, 4-CIN reduced astrocytic intracellular pH (pHi) slightly but alkalinized neuronal pHi. Nonetheless, pHi fell significantly in both cell types when they were treated with exogenous lactate, although 100 microM 4-CIN significantly reduced the magnitude of the acidosis in neurons but not astrocytes. Finally, 4-CIN treatment increased the uptake of a fluorescent 2-deoxy-D-glucose analog in neurons but did not alter the uptake rate of this 2-deoxy-D-glucose analog in astrocytes. These data confirm the existence of an astrocyte to neuron lactate shuttle in intact animals in the RTN, and lactate derived from astrocytes forms part of the central chemosensory stimulus for ventilation in this nucleus. When the lactate shuttle was disrupted by treatment with 4-CIN, neurons increased the uptake of glucose. Therefore, neurons seem to metabolize a combination of glucose and lactate (and other substances such as pyruvate) depending, in part, on the availability of each of these particular substrates.

  4. Thyroid hormone-regulated mouse cerebral cortex genes are differentially dependent on the source of the hormone: a study in monocarboxylate transporter-8- and deiodinase-2-deficient mice.

    PubMed

    Morte, Beatriz; Ceballos, Ainhoa; Diez, Diego; Grijota-Martínez, Carmen; Dumitrescu, Alexandra M; Di Cosmo, Caterina; Galton, Valerie Anne; Refetoff, Samuel; Bernal, Juan

    2010-05-01

    Thyroid hormones influence brain development through the control of gene expression. The concentration of the active hormone T(3) in the brain depends on T(3) transport through the blood-brain barrier, mediated in part by the monocarboxylate transporter 8 (Mct8/MCT8) and the activity of type 2 deiodinase (D2) generating T(3) from T(4). The relative roles of each of these pathways in the regulation of brain gene expression is not known. To shed light on this question, we analyzed thyroid hormone-dependent gene expression in the cerebral cortex of mice with inactivated Mct8 (Slc16a2) and Dio2 genes, alone or in combination. We used 34 target genes identified to be controlled by thyroid hormone in microarray comparisons of cerebral cortex from wild-type control and hypothyroid mice on postnatal d 21. Inactivation of the Mct8 gene (Mct8KO) was without effect on the expression of 31 of these genes. Normal gene expression in the absence of the transporter was mostly due to D2 activity because the combined disruption of Mct8 and Dio2 led to similar effects as hypothyroidism on the expression of 24 genes. Dio2 disruption alone did not affect the expression of positively regulated genes, but, as in hypothyroidism, it increased that of negatively regulated genes. We conclude that gene expression in the Mct8KO cerebral cortex is compensated in part by D2-dependent mechanisms. Intriguingly, positive or negative regulation of genes by thyroid hormone is sensitive to the source of T(3) because Dio2 inactivation selectively affects the expression of negatively regulated genes. PMID:20211971

  5. Expression of the hypoxia-inducible monocarboxylate transporter MCT4 is increased in triple negative breast cancer and correlates independently with clinical outcome

    SciTech Connect

    Doyen, J.; Trastour, C.; Ettore, F.; Peyrottes, I.; Toussant, N.; Gal, J.; Ilc, K.; Roux, D.; Parks, S.K.; Ferrero, J.M.; Pouysségur, J.

    2014-08-15

    Highlights: • Glycolytic markers are highly expressed in triple negative breast cancers. • Lactate/H{sup +} symporter MCT4 demonstrated the strongest deleterious impact on survival. • MCT4 should serve as a new prognostic factor in node-negative breast cancers. - Abstract: Background: {sup 18}Fluor-deoxy-glucose PET-scanning of glycolytic metabolism is being used for staging in many tumors however its impact on prognosis has never been studied in breast cancer. Methods: Glycolytic and hypoxic markers: glucose transporter (GLUT1), carbonic anhydrase IX (CAIX), monocarboxylate transporter 1 and 4 (MCT1, 4), MCT accessory protein basigin and lactate-dehydrogenase A (LDH-A) were assessed by immunohistochemistry in two cohorts of breast cancer comprising 643 node-negative and 127 triple negative breast cancers (TNBC) respectively. Results: In the 643 node-negative breast tumor cohort with a median follow-up of 124 months, TNBC were the most glycolytic (≈70%), followed by Her-2 (≈50%) and RH-positive cancers (≈30%). Tumoral MCT4 staining (without stromal staining) was a strong independent prognostic factor for metastasis-free survival (HR = 0.47, P = 0.02) and overall-survival (HR = 0.38, P = 0.002). These results were confirmed in the independent cohort of 127 cancer patients. Conclusion: Glycolytic markers are expressed in all breast tumors with highest expression occurring in TNBC. MCT4, the hypoxia-inducible lactate/H{sup +} symporter demonstrated the strongest deleterious impact on survival. We propose that MCT4 serves as a new prognostic factor in node-negative breast cancer and can perhaps act soon as a theranostic factor considering the current pharmacological development of MCT4 inhibitors.

  6. Modification of eucalyptus pulp fiber using silane coupling agents with aliphatic side chains of different length

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The objective of this work was to evaluate the effect of three silane coupling agents with different aliphatic chain lengths on the hydrophobicity of eucalyptus pulp fiber. The three silanes coupling agents used (isobutyltrimethoxysilane, methyltrimethoxysilane, and n-octyltriethoxysilane [OTES]) we...

  7. IN-SITU AQUIFER RESTORATION OF CHLORINATED ALIPHATICS BY METHANOTROPHIC BACTERIA

    EPA Science Inventory

    This project evaluated the potential of enhanced in-situ biotransformation of chlorinated aliphatic solvents by a bacterial community grown on methane under aerobic conditions. The target chlorinated compounds were trichloroethene (TCE), cis-and trans-1,2-dichloroethene (DCE), an...

  8. Joint Test Protocol for Validation of Alternatives to Aliphatic Isocyanate Polyurethanes

    NASA Technical Reports Server (NTRS)

    Lewis, Pattie

    2005-01-01

    The primary objective of this effort is to demonstrate and validate alternatives to aliphatic isocyanate polyurethanes. Successful completion of this project will result in one or more isocyanate-free coatings qualified for use at AFSPC and NASA installations participating in this project.

  9. PRECONCENTRATION OF ALIPHATIC AMINES FROM WATER DETERMINED BY CAPILLARY ELECTROPHORESIS WITH INDIRECT UV DETECTION

    EPA Science Inventory

    Preconcentration methodology based on adsorption chromatographies for enriching aliphatic amines (c1 to C4 substituted primary, secondary, and tertiary) and alkanolamines in water was studied by free zone capillary electrophoresis (CZE)with indirect UV detection. The solid-phase ...

  10. SELECTIVE ENUMERATION OF AROMATIC AND ALIPHATIC HYDROCARBON DEGRADING BACTERIA BY A MOST-PROBABLE-NUMBER PROCEDURE

    EPA Science Inventory

    A most-portable-number (MPN) procedure was developed to separately enumerate aliphatic and aromatic hydrocarbon degrading bacteria, because most of the currently available methods are unable to distinguish between these two groups. Separate 96-well microtiter plates are used to ...

  11. Spectrofluorimetric evaluation of total aliphatic and aromatic amines in well waters and wastewaters

    SciTech Connect

    Djozan, D.; Faraj-Zadeh, M.A.

    1998-09-01

    Aliphatic and aromatic amines are important metabolic intermediates in decomposition processes and are distributed in wastewaters. Monitoring of these compounds in the water samples can indicate whether the environmental waters are contaminated with wastewaters. A simple and rapid spectrofluorimetric method is described for the determination of aliphatic and aromatic amines on the basis of ammonia and aniline, respectively. Aromatic amines in samples were reacted at pH 5.5 with fluram immobilized on an Octadecylsilane Solid Phase Extraction (ODS-SPE) cartridge. The produced pyrrolinones were adsorbed on SPE and separated from the aliphatic amines. Analysis of these compounds was carried out by elution of SPE with 1 ml Tetrahydrofuran (THF) and determination of fluorescence intensity at excitation wavelength 400 nm and emission wavelength 475 nm. Aliphatic amines after passing from SPE were collected and reacted with fluram at pH 9.2, and extracted into dichloromethane at pH 3 and quantitated fluorimetrically. Linear dynamic ranges and detection limits (LOD) were 1-20, 0.43 mg l{sup {minus}1} and 1-200, 0.39 {micro}g l{sup {minus}1} for ammonia and aniline, respectively. The proposed method was successfully applied for the evaluation of these compounds in local well waters and municipality wastewaters.

  12. Copper-catalyzed aliphatic C-H amination with an amidine moiety.

    PubMed

    Chen, Hui; Sanjaya, Stephen; Wang, Yi-Feng; Chiba, Shunsuke

    2013-01-01

    A method for amination of aliphatic C-H bonds of N-alkylamidines is described that utilizes Cu(OAc)(2) as the catalyst in the presence of PhI(OAc)(2) and K(3)PO(4). The resulting products, dihydroimidazoles and tetrahydropyrimidines, could be converted into the corresponding diamines by hydride reduction. PMID:23252919

  13. Degradation of halogenated aliphatic compounds by Xanthobacter autotrophicus GJ10.

    PubMed Central

    Janssen, D B; Scheper, A; Dijkhuizen, L; Witholt, B

    1985-01-01

    A bacterium that is able to utilize a number of halogenated short-chain hydrocarbons and halogenated carboxylic acids as sole carbon source for growth was identified as a strain of Xanthobacter autotrophicus. The organism constitutively produces two different dehalogenases. One enzyme is specific for halogenated alkanes, whereas the other, which is more heat stable and has a higher pH optimum, is specific for halogenated carboxylic acids. Haloalkanes were hydrolyzed in cell extracts to produce alcohols and halide ions, and a route for the metabolism of 1,2-dichlorethane is proposed. Both dehalogenases show a broad substrate specificity, allowing the degradation of bromine- and chlorine-substituted organic compounds. The results show that X. autotrophicus may play a role in the degradation of organochlorine compounds and that hydrolytic dehalogenases may be involved in the microbial metabolism of short-chain halogenated hydrocarbons in microorganisms. Images PMID:3994371

  14. Matrix-assisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers using new ionic liquid matrices.

    PubMed

    Serrano, Carlos A; Zhang, Yi; Yang, Jian; Schug, Kevin A

    2011-05-15

    In this study, two novel ionic liquid matrices (ILMs), N,N-diisopropylethylammonium 3-oxocoumarate and N,N-diisopropylethylammonium dihydroxymonooxoacetophenoate, were tested for the structural elucidation of recently developed aliphatic biodegradable polymers by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The polymers, formed by a condensation reaction of three components, citric acid, octane diol, and an amino acid, are fluorescent, but the exact mechanism behind their luminescent properties has not been fully elucidated. In the original studies, which introduced the polymer class (J. Yang et al., Proc. Natl. Acad. Sci. USA 2009, 106, 10086-10091), a hyper-conjugated cyclic structure was proposed as the source for the photoluminescent behavior. With the use of the two new ILMs, we present evidence that supports the presence of the proposed cyclization product. In addition, the new ILMs, when compared with a previously established ILM, N,N-diisopropylethylammonium α-cyano-3-hydroxycinnimate, provided similar signal intensities and maintained similar spectral profiles. This research also established that the new ILMs provided good spot-to-spot reproducibility and high ionization efficiency compared with corresponding crystalline matrix preparations. Many polymer features revealed through the use of the ILMs could not be observed with crystalline matrices. Ultimately, the new ILMs highlighted the composition of the synthetic polymers, as well as the loss of water that was expected for the formation of the proposed cyclic structure on the polymer backbone.

  15. Biodegradation of individual and multiple chlorinated aliphatic hydrocarbons by methane-oxidizing cultures.

    PubMed Central

    Chang, H L; Alvarez-Cohen, L

    1996-01-01

    The microbial degradation of chlorinated and nonchlorinated methanes, ethanes, and ethanes by a mixed methane-oxidizing culture grown under chemostat and batch conditions is evaluated and compared with that by two pure methanotrophic strains: CAC1 (isolated from the mixed culture) and Methylosinus trichosporium OB3b. With the exception of 1,1-dichloroethylene, the transformation capacity (Tc) for each chlorinated aliphatic hydrocarbon was generally found to be in inverse proportion to its chlorine content within each aliphatic group (i.e., methanes, ethanes, and ethenes), whereas similar trends were not observed for degradation rate constants. Tc trends were similar for all methane-oxidizing cultures tested. None of the cultures were able to degrade the fully chlorinated aliphatics such as perchloroethylene and carbon tetrachloride. Of the four cultures tested, the chemostat-grown mixed culture exhibited the highest Tc for trichloroethylene, cis-1,2-dichloroethylene, tetrachloroethane, 1,1,1-trichloroethane, and 1,2-dichloroethane, whereas the pure batch-grown OB3b culture exhibited the highest Tc for all other compounds tested. The product toxicity of chlorinated aliphatic hydrocarbons in a mixture containing multiple compounds was cumulative and predictable when using parameters measured from the degradation of individual compounds. The Tc for each chlorinated aliphatic hydrocarbon in a mixture (Tcmix) and the total Tc for the mixture (sigma Tcmix) are functions of the individual Tc, the initial substrate concentration (S0), and the first-order rate constant (k/Ks) of each compound in the mixture, indicating the importance of identifying the properties and compositions of all potentially degradable compounds in a contaminant mixture. PMID:8795228

  16. Telomerization of amino acids with butadiene, catalyzed by palladium complexes

    SciTech Connect

    Dzhemilev, U.M.; Fakhretdinov, R.N.; Telin, A.G.

    1987-01-10

    The telomerization of ..cap alpha..-, ..beta..-, ..gamma..-, and epsilon-amino acids having various structures with butadiene under the influence of the three-component palladium catalyst Pd(acac)/sub 2/-PPh/sub 3/-AlEt/sub 3/ was investigated in DMSO-toluene solution. The ..cap alpha..- and epsilon-aliphatic and also the ..cap alpha..-, ..beta..-, and ..gamma..-aromatic amino acids react with butadiene, giving the products from octadienylation at the amino group exclusively. Under the conditions of telomerization aliphatic ..beta..-amino acids are cleaved with the formation of unsaturated tertiary amines. In the case of aliphatic ..gamma..-amino acids it is possible to obtain telomers alkylated at the carbonyl group.

  17. Aliphatic β-nitroalcohols for therapeutic corneoscleral cross-linking: corneal permeability considerations

    PubMed Central

    Wen, Quan; Trokel, Stephen L.; Paik, David C.

    2012-01-01

    Introduction Our recent tissue cross-linking studies have raised the possibility of using aliphatic β-nitro alcohols (BNAs) for pharmacologic, therapeutic corneal cross-linking. The present study was performed in order to determine the permeability of BNAs and to explore the use of permeability enhancing agents. Methods Ex vivo rabbit corneas were mounted in a typical Franz diffusion chamber. BNA permeability was determined by assaying the recipient chamber over time using a modification of the Griess nitrite colorimetric assay. The apparent permeability coefficient (Ptot) was determined for 2 mono-nitroalcohols, 2-nitroethanol (2NE) and 2-nitro-1-propanol (2NProp); a nitro-diol (2-methyl-2-nitro-1,3-propanediol=MNPD); and a nitro-triol (2-hydroxymethyl-2-nitro-1,3-propanediol=HNPD). Permeability enhancing effects using benzalkonium chloride (BAC) [0.01 and 0.02%], ethylenediaminetetraacetic acid (EDTA) [0.05%], and a combination of BAC 0.01% + tetracaine (TC) [0.5%] were also studied. Results The Ptot (+/−S.E.) values (cm/sec) were as follows: Ptot=4.33×10−5 (+/−9.82×10−6) for 2NE (MW=91), Ptot=9.34×10−6 (+/− 2.16×10−7) for 2NProp (MW=105), Ptot=4.37×10−6 (+/− 1.86×10−7) for MNPD (MW=135), and Ptot=8.95×10−7 (+/−1.93×10−8) for HNPD (MW=151). Using the nitrodiol, permeability increased approximately two-fold using BAC 0.01%, five-fold using BAC 0.02% and five-fold using the combination of BAC 0.01% + TC 0.5%. No effect was observed using EDTA 0.05%. Conclusions The results indicate that the corneal epithelium is permeable to BNAs with the apparent permeability corresponding to molecular weight. The findings are consistent with previous literature indicating that the small size of these compounds (<10Å) favors their passage through the corneal epithelium via the paracellular route. This information will help to guide dosing regimens for in vivo topical cross-linking studies. PMID:22868628

  18. 40 CFR 721.530 - Substituted aliphatic acid halide (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... hydrolysis product is less than 10 ppm prior to discharge or purifying the waste stream so that the first hydrolysis product is less than 10 ppm. Those purified waste streams may be reused or sold. All of...

  19. 40 CFR 721.530 - Substituted aliphatic acid halide (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... hydrolysis product is less than 10 ppm prior to discharge or purifying the waste stream so that the first hydrolysis product is less than 10 ppm. Those purified waste streams may be reused or sold. All of...

  20. 40 CFR 721.530 - Substituted aliphatic acid halide (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... the substance by chemically treating liquid wastes so that the first hydrolysis product is less than 10 ppm prior to discharge or purifying the waste stream so that the first hydrolysis product is...

  1. 40 CFR 721.530 - Substituted aliphatic acid halide (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... hydrolysis product is less than 10 ppm prior to discharge or purifying the waste stream so that the first hydrolysis product is less than 10 ppm. Those purified waste streams may be reused or sold. All of...

  2. 40 CFR 721.530 - Substituted aliphatic acid halide (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... hydrolysis product is less than 10 ppm prior to discharge or purifying the waste stream so that the first hydrolysis product is less than 10 ppm. Those purified waste streams may be reused or sold. All of...

  3. Aliphatic components of coal. Quarterly report, March-June 1980

    SciTech Connect

    Deno, N.C.; Cannon, C.; Curry, K.; Jones, A.D.; Potter, T.C.; Rakitsky, W.G.; Wagner, K.; Yevak, R.

    1980-06-01

    Liquefaction of coal involves thermolysis of benzyl-oxygen and/or benzyl-benzyl bonds as the first step in the depolymerization. This view derives from NMR studies, studies with model compounds, and oxidative degradations with Na/sub 2/Cr/sub 2/O/sub 7/ and CF/sub 3/CO/sub 3/H/sub 2/. The best method for determining the amount of arylmethyl groups in coals is from the yield of acetic acid formed in oxidative degradation with CF/sub 3/CO/sub 3/H-H/sub 2/SO/sub 4/. The following observations and interpretations are made: a sharp increase in arylmethyl accompanies liquefaction in all five coals and in two coals studied earlier. This increase is the result of thermal cleavage to benzyl radicals and abstraction of hydrogen atoms by the benzyl radicals to form arylmethyl. All five coals give about the same percentage increase in arylmethyl after 90 mins of solvent refining, but not after 3 mins. This indicates that benzyl radicals form from more than one type of structure. Based on studies of model compounds, it is attractive to ascribe arylmethyl formation in 3 mins to cleavage of benzyl ethers and slower cleavage to bibenzyl structures. It might have been expected that the more arylmethyl, the more cleavage, and the more SRC. In fact the opposite is found. The conflict would be resolved if coal liquefaction depended more on certain critical cleavages and the conversion of a 3-dimensional polymer to a 1-dimensional polymer than on the total amount of cleavage and the extent of depolymerization. The amount of arylmethyl in the residue (3 min) is about the same as in the original coal. This indicates that arylmethyls do not play any role in liquefaction as expected. No higher homologs of acetic acid were observed indicating the absence of arylalkyls above methyl.

  4. Genetic adaptation of bacteria to halogenated aliphatic compounds.

    PubMed Central

    Janssen, D B; van der Ploeg, J R; Pries, F

    1995-01-01

    The bacterial degradation and detoxification of chlorinated xenobiotic compounds requires the production of enzymes that are capable of recognizing and converting compounds which do not occur at significant concentrations in nature. We have studied the catabolic route of 1,2-dichloroethane as an example of a pathway for the conversion of such a synthetic compound. In strains of Xanthobacter and Ancylobacter that have been isolated on 1,2-dichloroethane, the first catabolic step is catalyzed by a hydrolytic haloalkane dehalogenase. The enzyme converts 1,2-dichloroethane to 2-chloroethanol but is also active with many other environmentally important haloalkanes such as methylchloride, methylbromide, 1,2-dibromoethane, epichlorohydrin, and 1,3-dichloropropene. Further degradation of 2-chloroethanol proceeds by oxidation to the carboxylic acid and dehalogenation to glycolate. The aldehyde dehydrogenase prevents toxicity of the reactive chloroacetaldehyde that is formed as an intermediate and is necessary for establishing a functional 2-chloroethanol degradative pathway in a strain that is not capable of growth on this compound. PMID:8565904

  5. Genetic adaptation of bacteria to halogenated aliphatic compounds

    SciTech Connect

    Janssen, D.B.; Ploeg, J.R. van der; Pries, F.

    1995-06-01

    The bacterial degradation and detoxification of chlorinated xenobiotic compounds requires the production of enzymes that are capable of recognizing and converting compounds which do not occur at significant concentrations in nature. We have studied the catabolic route of 1,2-dichloroethane as an example of a pathway for the conversion of such a synthetic compound. In strains of Xanthobacter and Ancylobacter that have been isolated on 1,2-dichloroethane, the first catabolic step is catalyzed by a hydrolytic haloalkane dehalogenase. The enzyme converts 1,2-dichloroethane to 2-chloroethanol but is also active with many other environmentally important haloalkanes such as methylchloride, methylbromide, 1,2-dibromoethane, epichlorohydrin, and 1,3-dichloropropene. Further degradation of 2-chloroethanol proceeds by oxidation to the carboxylic acid and dehalogenation to glycolate. The aldehyde dehydrogenase prevents toxicity of the reactive chloroacetaldehyde that is formed as an intermediate and is necessary for establishing a functional 2-chloroethanol degradative pathway in a strain that is not capable of growth on this compound. 27 refs., 3 figs., 1 tab.

  6. Genetic adaptation of bacteria to halogenated aliphatic compounds.

    PubMed

    Janssen, D B; van der Ploeg, J R; Pries, F

    1995-06-01

    The bacterial degradation and detoxification of chlorinated xenobiotic compounds requires the production of enzymes that are capable of recognizing and converting compounds which do not occur at significant concentrations in nature. We have studied the catabolic route of 1,2-dichloroethane as an example of a pathway for the conversion of such a synthetic compound. In strains of Xanthobacter and Ancylobacter that have been isolated on 1,2-dichloroethane, the first catabolic step is catalyzed by a hydrolytic haloalkane dehalogenase. The enzyme converts 1,2-dichloroethane to 2-chloroethanol but is also active with many other environmentally important haloalkanes such as methylchloride, methylbromide, 1,2-dibromoethane, epichlorohydrin, and 1,3-dichloropropene. Further degradation of 2-chloroethanol proceeds by oxidation to the carboxylic acid and dehalogenation to glycolate. The aldehyde dehydrogenase prevents toxicity of the reactive chloroacetaldehyde that is formed as an intermediate and is necessary for establishing a functional 2-chloroethanol degradative pathway in a strain that is not capable of growth on this compound.

  7. Genetic adaptation of bacteria to halogenated aliphatic compounds.

    PubMed

    Janssen, D B; van der Ploeg, J R; Pries, F

    1995-06-01

    The bacterial degradation and detoxification of chlorinated xenobiotic compounds requires the production of enzymes that are capable of recognizing and converting compounds which do not occur at significant concentrations in nature. We have studied the catabolic route of 1,2-dichloroethane as an example of a pathway for the conversion of such a synthetic compound. In strains of Xanthobacter and Ancylobacter that have been isolated on 1,2-dichloroethane, the first catabolic step is catalyzed by a hydrolytic haloalkane dehalogenase. The enzyme converts 1,2-dichloroethane to 2-chloroethanol but is also active with many other environmentally important haloalkanes such as methylchloride, methylbromide, 1,2-dibromoethane, epichlorohydrin, and 1,3-dichloropropene. Further degradation of 2-chloroethanol proceeds by oxidation to the carboxylic acid and dehalogenation to glycolate. The aldehyde dehydrogenase prevents toxicity of the reactive chloroacetaldehyde that is formed as an intermediate and is necessary for establishing a functional 2-chloroethanol degradative pathway in a strain that is not capable of growth on this compound. PMID:8565904

  8. Biodegradation of aliphatic hydrocarbons in the presence of hydroxy cucurbit[6]uril.

    PubMed

    Pasumarthi, Rajesh; Kumar, Vikash; Chandrasekharan, Sivaraman; Ganguly, Anasuya; Banerjee, Mainak; Mutnuri, Srikanth

    2014-11-15

    Aliphatic hydrocarbons are one of the major environmental pollutants with reduced bioavailability. The present study focuses on the effect of hydroxy cucurbit[6]uril on the bioavailability of hydrocarbons. A bacterial consortium was used for biodegradation studies under saline and non-saline conditions. Based on denaturing gradient gel electrophoresis results it was found that the consortium under saline conditions had two different strains. The experiment was conducted in microcosms with tetradecane, hexadecane, octadecane and mixture of the mentioned hydrocarbons as the sole carbon source. The residual hydrocarbon was quantified using gas chromatography every 24h. It was found that biodegradation of tetradecane and hexadecane, as individual carbon source increased in the presence of hydroxy CB[6], probably due to the increase in their bioavailability. In case of octadecane this did not happen. Bioavailability of all three aliphatic hydrocarbons was increased when provided as a mixture to the consortium under saline conditions.

  9. Synthesis and Bioactivity of 5-Substituted-2-furoyl Diacylhydazide Derivatives with Aliphatic Chain

    PubMed Central

    Cui, Zining; Li, Xinghai; Tian, Fang; Yan, Xiaojing

    2014-01-01

    A series of 5-substituted-2-furoyl diacylhydazide derivatives with aliphatic chain were designed and synthesized. Their structures were characterized by IR, 1H NMR, elemental analysis, and X-ray single crystal diffraction. The anti-tumor bioassay revealed that some title compounds exhibited promising activity against the selected cancer cell lines, especially against the human promyelocytic leukemic cells (HL-60). Their fungicidal tests indicated that most of the title compounds showed significant anti-fungal activity. The preliminary structure-activity relationship showed that the aliphatic chain length and differences in the R2 group had obvious effects on the anti-tumor and anti-fungal activities. The bioassay results demonstrated that the title compounds hold great promise as novel lead compounds for further drug discovery. PMID:24853128

  10. Chiral surfactant-type catalyst: enantioselective reduction of long-chain aliphatic ketoesters in water.

    PubMed

    Lin, Zechao; Li, Jiahong; Huang, Qingfei; Huang, Qiuya; Wang, Qiwei; Tang, Lei; Gong, Deying; Yang, Jun; Zhu, Jin; Deng, Jingen

    2015-05-01

    A series of amphiphilic ligands were designed and synthesized. The rhodium complexes with the ligands were applied to the asymmetric transfer hydrogenation of broad range of long-chained aliphatic ketoesters in neat water. Quantitative conversion and excellent enantioselectivity (up to 99% ee) was observed for α-, β-, γ-, δ- and ε-ketoesters as well as for α- and β-acyloxyketone using chiral surfactant-type catalyst 2. The CH/π interaction and the strong hydrophobic interaction of long aliphatic chains between the catalyst and the substrate in the metallomicelle core played a key role in the catalytic transition state. Synergistic effects between the metal-catalyzed site and the hydrophobic microenvironment of the core in the micelle contributed to high stereoselectivity.

  11. [Synthesis, characterization and fluorescent properties of copper phthalocyanine derivates substituted by aliphatic alcohol].

    PubMed

    Zhang, Liang; Xu, Qing-Feng; Lu, Jian-Mei; Yao, She-Chun

    2007-04-01

    A series of copper phthalocyanine derivatives substituted by aliphatic chain were obtained by the reaction of tetra-formyl chloride copper phthalocyanine and aliphatic alcohol such as n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, n-caprylic alcohol and lauryl alcohol. IR, UV-Vis, elemental analysis and 1H NMR verified the structures and substituting degree. The solubility and the relationship between fluorescence and concentration and substituting group were studied in organic solution. It was confirmed that the solubility in organic solution was improved greatly, the fluorescence did not change in linear according to the concentration and the fluorescence of copper phthalocyanine derivatives substituted by the long alkyl was stronger than that substituted by the relatively short alkyl.

  12. Friction of iron lubricated with aliphatic and aromatic hydrocarbons and halogenated analogs

    NASA Technical Reports Server (NTRS)

    Buckley, D. H.

    1976-01-01

    The influence of oxygen and various organic molecules on the reduction of the friction of an iron (011) single crystal surface was investigated. A comparison was made between aliphatic and aromatic structures, all of which contained six carbon atoms, and among various halogen atoms. Results of the investigation indicate that hexane and benzene give similar friction coefficients over a range of loads except at very light loads. At light loads, the friction decreased with an increase in the load where the halogens fluorine and chlorine are incorporated into the benzene molecular structure; however, over the same load range when bromine and iodine were present, the friction was relatively unchanged. The aliphatic compound chlorohexane exhibited lower friction coefficients than the aromatic structure chlorobenzene at very light loads. With the brominated benzene structures, however, friction was essentially the same. Oxygen was more effective in reducing friction than were the simple hydrocarbons.

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

    NASA Technical Reports Server (NTRS)

    Langford, Shannon D.

    2007-01-01

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

  14. Biodegradation of aliphatic hydrocarbons in the presence of hydroxy cucurbit[6]uril.

    PubMed

    Pasumarthi, Rajesh; Kumar, Vikash; Chandrasekharan, Sivaraman; Ganguly, Anasuya; Banerjee, Mainak; Mutnuri, Srikanth

    2014-11-15

    Aliphatic hydrocarbons are one of the major environmental pollutants with reduced bioavailability. The present study focuses on the effect of hydroxy cucurbit[6]uril on the bioavailability of hydrocarbons. A bacterial consortium was used for biodegradation studies under saline and non-saline conditions. Based on denaturing gradient gel electrophoresis results it was found that the consortium under saline conditions had two different strains. The experiment was conducted in microcosms with tetradecane, hexadecane, octadecane and mixture of the mentioned hydrocarbons as the sole carbon source. The residual hydrocarbon was quantified using gas chromatography every 24h. It was found that biodegradation of tetradecane and hexadecane, as individual carbon source increased in the presence of hydroxy CB[6], probably due to the increase in their bioavailability. In case of octadecane this did not happen. Bioavailability of all three aliphatic hydrocarbons was increased when provided as a mixture to the consortium under saline conditions. PMID:25277552

  15. NEW ALIPHATIC ESTER, β-SITOSTEROL DIGLUCOSIDE AND VESICARIA BIFLAVONES FROM THE SEEDS OF RUMEX VESICARIUS L.

    PubMed

    Siddiqui, Abdul Wadood; Ali, Mohammed; Naquvi, Kamran J; Husain, Shahnaz S

    2015-01-01

    Rumex vesicalius L. (Polygonaceae) is an annual, monoecious, glabrous, pale green herb cultivated as a leafy vegetable in south western Asia and northern Africa. Its seeds are prescribed as a refrigerant, laxa- tive, antidote for scorpion venom and to cure dysentery and liver diseases. Phytochemical investigation of a methanolic extract of the seeds of R. vesicarius resulted in the isolation of a new aliphatic ester n-heptacosanyl n-hexanoate (2), a steroidal diglucoside stigmasta-5-en-3-ol-3-O-β-D-glucopyranosido-(4--->1")-O-β-D-glu- copyranoside (3) and two bioflavonoids characterized as (2a,3a-trans)-3a(β),5a,7a,3'a,4'a-pentahydroxyfla- vanolyl-(8a-2')-5,7,3'-trihydroxy-4'-methoxy-8-n-but-3"-enyl-flavanone (4) and 5,7,3',4',5'-pentahydroxy- 8-(cis-1" α,2"β-dihydroxyhept-4"-enyl-7"-oic acid)-flavanoyl-(2'--8a)-5a,7a,3'a,5'a-tetrahydroxy-4'a- methoxyflavanone (5) together with stigmasterol (1). The structures of all the isolated phytoconstituents have been established on the basis of spectral data analysis and chemical reactions. PMID:26665404

  16. Dechlorination of trichlorofluoromethane (CFC-11) by sulfate-reducing bacteria from an aquifer contaminated with halogenated aliphatic compounds.

    PubMed Central

    Sonier, D N; Duran, N L; Smith, G B

    1994-01-01

    Groundwater samples were obtained from a deep aquifer contaminated with halogenated aliphatic compounds. One-milliliter samples contained 9.2 x 10(5) total bacteria (by acridine orange microscopic counts) and 2.5 x 10(3) sulfate-reducing bacteria (by most probable number analysis). Samples were incubated anaerobically in a basal salts medium with acetate as the electron donor and nitrate and sulfate as the electron acceptors. Residual levels of trichlorofluoromethane (CFC-11) in samples were biotically degraded, while trichloroethylene was not. When successively higher levels of CFC-11 were added, increasingly rapid degradation rates were observed. Concomitant with CFC-11 degradation was the near stoichiometric production of fluorodichloromethane (HCFC-21); the production of HCFC-21 was verified by mass spectrometry. CFC-11 degradation was dependent on the presence of acetate (or butyrate) and sulfate but was independent of nitrate. Other carbon sources such as lactate and isopropanol did not support the degradation. The addition of 1 mM sodium sulfide completely inhibited CFC-11 degradation; however, degradation occurred in the presence of 2 mM 2-bromoethanesulfonic acid. These results indicate that the anaerobic dechlorination of CFC-11 is carried out by sulfate-reducing bacteria and not by denitrifying or methanogenic bacteria. Images PMID:7811093

  17. Controlled oxidation of aliphatic CH bonds in metallo-monooxygenases: mechanistic insights derived from studies on deuterated and fluorinated hydrocarbons.

    PubMed

    Chen, Yao-Sheng; Luo, Wen-I; Yang, Chung-Ling; Tu, Yi-Jung; Chang, Chun-Wei; Chiang, Chih-Hsiang; Chang, Chi-Yao; Chan, Sunney I; Yu, Steve S-F

    2014-05-01

    The control over the regio- and/or stereo-selective aliphatic CH oxidation by metalloenzymes is of great interest to scientists. Typically, these enzymes invoke host-guest chemistry to sequester the substrates within the protein pockets, exploiting sizes, shapes and specific interactions such as hydrogen-bonding, electrostatic forces and/or van der Waals interactions to control the substrate specificity, regio-specificity and stereo-selectivity. Over the years, we have developed a series of deuterated and fluorinated variants of these hydrocarbon substrates as probes to gain insights into the controlled CH oxidations of hydrocarbons facilitated by these enzymes. In this review, we illustrate the application of these designed probes in the study of three monooxygenases: (i) the particulate methane monooxygenase (pMMO) from Methylococcus capsulatus (Bath), which oxidizes straight-chain C1-C5 alkanes and alkenes to form their corresponding 2-alcohols and epoxides, respectively; (ii) the recombinant alkane hydroxylase (AlkB) from Pseudomonas putida GPo1, which oxidizes the primary CH bonds of C5-C12 linear alkanes; and (iii) the recombinant cytochrome P450 from Bacillus megaterium, which oxidizes C12-C20 fatty acids at the ω-1, ω-2 or ω-3 CH positions.

  18. Dechlorination of trichlorofluoromethane (CFC-11) by sulfate-reducing bacteria from an aquifer contaminated with halogenated aliphatic compounds.

    PubMed

    Sonier, D N; Duran, N L; Smith, G B

    1994-12-01

    Groundwater samples were obtained from a deep aquifer contaminated with halogenated aliphatic compounds. One-milliliter samples contained 9.2 x 10(5) total bacteria (by acridine orange microscopic counts) and 2.5 x 10(3) sulfate-reducing bacteria (by most probable number analysis). Samples were incubated anaerobically in a basal salts medium with acetate as the electron donor and nitrate and sulfate as the electron acceptors. Residual levels of trichlorofluoromethane (CFC-11) in samples were biotically degraded, while trichloroethylene was not. When successively higher levels of CFC-11 were added, increasingly rapid degradation rates were observed. Concomitant with CFC-11 degradation was the near stoichiometric production of fluorodichloromethane (HCFC-21); the production of HCFC-21 was verified by mass spectrometry. CFC-11 degradation was dependent on the presence of acetate (or butyrate) and sulfate but was independent of nitrate. Other carbon sources such as lactate and isopropanol did not support the degradation. The addition of 1 mM sodium sulfide completely inhibited CFC-11 degradation; however, degradation occurred in the presence of 2 mM 2-bromoethanesulfonic acid. These results indicate that the anaerobic dechlorination of CFC-11 is carried out by sulfate-reducing bacteria and not by denitrifying or methanogenic bacteria. PMID:7811093

  19. NEW ALIPHATIC ESTER, β-SITOSTEROL DIGLUCOSIDE AND VESICARIA BIFLAVONES FROM THE SEEDS OF RUMEX VESICARIUS L.

    PubMed

    Siddiqui, Abdul Wadood; Ali, Mohammed; Naquvi, Kamran J; Husain, Shahnaz S

    2015-01-01

    Rumex vesicalius L. (Polygonaceae) is an annual, monoecious, glabrous, pale green herb cultivated as a leafy vegetable in south western Asia and northern Africa. Its seeds are prescribed as a refrigerant, laxa- tive, antidote for scorpion venom and to cure dysentery and liver diseases. Phytochemical investigation of a methanolic extract of the seeds of R. vesicarius resulted in the isolation of a new aliphatic ester n-heptacosanyl n-hexanoate (2), a steroidal diglucoside stigmasta-5-en-3-ol-3-O-β-D-glucopyranosido-(4--->1")-O-β-D-glu- copyranoside (3) and two bioflavonoids characterized as (2a,3a-trans)-3a(β),5a,7a,3'a,4'a-pentahydroxyfla- vanolyl-(8a-2')-5,7,3'-trihydroxy-4'-methoxy-8-n-but-3"-enyl-flavanone (4) and 5,7,3',4',5'-pentahydroxy- 8-(cis-1" α,2"β-dihydroxyhept-4"-enyl-7"-oic acid)-flavanoyl-(2'--8a)-5a,7a,3'a,5'a-tetrahydroxy-4'a- methoxyflavanone (5) together with stigmasterol (1). The structures of all the isolated phytoconstituents have been established on the basis of spectral data analysis and chemical reactions.

  20. Close correlation between heat shock response and cytotoxicity in Neurospora crassa treated with aliphatic alcohols and phenols

    SciTech Connect

    Meyer, U.; Schweim, P.; Fracella, F.; Rensing, L.

    1995-03-01

    In Neurospora crassa the aliphatic alcohols methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, ethylene glycol, glycerol, and allyl alcohol and the phenolic compounds phenol, hydroquinone, resorcinol, pyrogallol, phloroglucinol, sodium salicylate, and acetylsalicylic acid were analyzed with respect to their capacities to induce heat shock proteins (HSP) and to inhibit protein synthesis. Both the alcohols and phenols showed the greatest levels of HSP induction at concentrations which inhibited the overall protein synthesis by about 50%. The abilities of the different alcohols to induce the heat shock response are proportional to their lipophilicities: the lipophilic alcohol isobutanol is maximally inductive at about 0.6 M, whereas the least lipophilic alcohol, methanol, causes maximal induction at 5.7 M. The phenols, in general, show a higher capability to induce the heat shock response. The concentrations for maximal induction range between 25 mM (sodium salicylate) and 100 mM (resorcinol). Glycerol (4.1 M) shifted the concentration necessary for maximal HSP induction by hydroquinone from 50 to 200 mM. The results reveal that the induction of HSP occurs under conditions which considerably constrain cell metabolism. The heat shock response, therefore, does not represent a sensitive marker for toxicity tests but provides a good estimate for the extent of cell damage.

  1. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    DOEpatents

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-09-29

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase is dispersed.

  2. Coefficients of caffeine distribution in aliphatic alcohol-ammonium sulfate-water systems

    NASA Astrophysics Data System (ADS)

    Korenman, Ya. I.; Krivosheeva, O. A.; Mokshina, N. Ya.

    2012-11-01

    The extraction of caffeine with aliphatic alcohols C3-C9 from aqueous solutions in the presence of a salting-out agent (ammonium sulfate) is studied. Quantitative characteristics of extraction are calculated: the distribution coefficients ( D) and the degree of recovery ( R, %). Relations are found between log D of caffeine and the length of the hydrocarbon radical in the alcohol molecule, along with certain physicochemical properties of the extragents.

  3. Degradation of halogenated aliphatic compounds by the ammonia- oxidizing bacterium Nitrosomonas europaea.

    PubMed Central

    Vannelli, T; Logan, M; Arciero, D M; Hooper, A B

    1990-01-01

    Suspensions of Nitrosomonas europaea catalyzed the ammonia-stimulated aerobic transformation of the halogenated aliphatic compounds dichloromethane, dibromomethane, trichloromethane (chloroform), bromoethane, 1,2-dibromoethane (ethylene dibromide), 1,1,2-trichloroethane, 1,1,1-trichloroethane, monochloroethylene (vinyl chloride), gem-dichloroethylene, cis- and trans-dichloroethylene, cis-dibromoethylene, trichloroethylene, and 1,2,3-trichloropropane, Tetrachloromethane (carbon tetrachloride), tetrachloroethylene (perchloroethylene), and trans-dibromoethylene were not degraded. PMID:2339874

  4. Diverse Asymmetric Hydrofunctionalization of Aliphatic Internal Alkenes through Catalytic Regioselective Hydroboration.

    PubMed

    Xi, Yumeng; Hartwig, John F

    2016-06-01

    We report a two-step strategy for diverse hydrofunctionalizations of aliphatic internal alkenes with high regioselectivity and enantioselectivity. This process comprises a copper-catalyzed asymmetric hydroboration and subsequent stereospecific derivatizations of the secondary boronates. By this strategy, a range of compounds, such as amides, alkyl fluorides and bromides, alcohols, aldehydes, arenes, and heteroarenes, were synthesized from an internal alkene with high regioselectivity and enantioselectivity. Computational studies provide insight into the origins of these selectivities. PMID:27167490

  5. Derivatization to stabilize some aliphatic primary hydroxylamines for g.l.c. analysis.

    PubMed

    Beckett, A H; Achari, R

    1977-04-01

    By appropriate choice of trimethylsilylating and trifluoroacetylating reagents and organic solvents for extraction, stable derivative of aliphatic primary hydroxylamines metabolites, N-hydroxyphentermine, N-hydroxychlorphentermine, N-hydroxymexiletene, N-hydroxyphenethylamine, N-hydroxyamphetamine, and N-hydroxy-3,4-dimethoxyamphetamine, were obtained and examined by g.l.c. analysis without decomposition and without interference from the parent drug or other metabolic products. PMID:17670

  6. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    SciTech Connect

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-03-17

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase id dispersed.

  7. BIOTRANSFORMATION OF MIXTURES OF CHLORINATED ALIPHATIC HYDROCARBONS BY AN ACETATE-GROWN METHANOGENIC ENRICHMENT CULTURE. (R825549C053)

    EPA Science Inventory

    Biotransformation of chlorinated aliphatic hydrocarbons under anaerobic conditions has received considerable attention due to the prevalence of these compounds as groundwater contaminants. However, information concerning the impact of mixtures of chlorinated compounds on their...

  8. Unique gas and hydrocarbon adsorption in a highly porous metal-organic framework made of extended aliphatic ligands.

    PubMed

    Li, Kunhao; Lee, Jeongyong; Olson, David H; Emge, Thomas J; Bi, Wenhua; Eibling, Matthew J; Li, Jing

    2008-12-14

    High and unique gas and hydrocarbon adsorption in a highly stable guest-free microporous metal-organic framework constructed on rigid aliphatic ligands, H(2)bodc and ted, is reported in this work. PMID:19082093

  9. DETERMINATION OF ALIPHATIC AMINES IN WATER USING DERIVATIZATION WITH FLUORESCEIN ISOTHIOCYANATE AND CAPILLARY ELECTROPHORESIS/LASER-INDUCED FLUORESCENCE DETECTION.

    EPA Science Inventory

    Detection-oriented derivatization of aliphatic amines and amine functional groups in coumpounds of environmental interest was studied using fluorescein isothiocyanate (FITC) with separation/determination by capillary electrophoresis/laser-induced fluorescence. Determinative level...

  10. A laboratory investigation of the effectiveness of various skin and surface decontaminants for aliphatic polyisocyanates.

    PubMed

    Bello, Dhimiter; Woskie, Susan R; Streicher, Robert P; Stowe, Meredith H; Sparer, Judy; Redlich, Carrie A; Cullen, Mark R; Liu, Youcheng

    2005-07-01

    Isocyanates may cause contact dermatitis and respiratory sensitization leading to asthma. Dermal exposure to aliphatic isocyanates in auto body shops is very common. However, little is known about the effectiveness of available commercial products used for decontaminating aliphatic polyisocyanates. This experimental study evaluated the decontamination effectiveness of aliphatic polyisocyanates for several skin and surface decontaminants available for use in the auto body industry. The efficiency of two major decontamination mechanisms, namely (i) consumption of free isocyanate groups via chemical reactions with active hydrogen components of the decontaminant and (ii) physical removal processes such as dissolution were studied separately for each decontaminant. Considerable differences were observed among surface decontaminants in their rate of isocyanate consumption, of which those containing free amine groups performed the best. Overall, Pine-Sol(R) MEA containing monoethanolamine was the most efficient surface decontaminant, operating primarily via chemical reaction with the isocyanate group. Polypropylene glycol (PPG) had the highest physical removal efficiency and the lowest reaction rate with isocyanates. All tested skin decontaminants performed similarly, accomplishing decontamination primarily via physical processes and removing 70-80% of isocyanates in one wiping. Limitations of these skin decontaminants are discussed and alternatives presented. In vitro testing using animal skins and in vivo testing with field workers are being conducted to further assess the efficiency and identify related determinants. PMID:15986052

  11. Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

    PubMed

    Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S

    2016-05-15

    This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided.

  12. Self-assembled aliphatic chain extended polyurethane nanobiohybrids: emerging hemocompatible biomaterials for sustained drug delivery.

    PubMed

    Mishra, Abhinay; Singh, Sunil K; Dash, Debabrata; Aswal, Vinod K; Maiti, Biswajit; Misra, Manjusri; Maiti, Pralay

    2014-05-01

    Novel polyurethanes (PUs) have been synthesized using an aliphatic diisocyanate and aliphatic chain extenders with varying chain length. Nanocomposites of PUs have been prepared by dispersing 2-D nanoclay in poly-ol followed by prepolymerization and subsequent chain extension using various chain extenders. Systematic improvement in toughness and adequate enhancement in stiffness in the presence of nanoclay has been observed for PUs with longer chain extenders, and these new classes of nanocomposites exhibit no toughness-stiffness trade-off. Bottom-up self-assembly starting from the molecular level to micron-scale crystallite has been revealed through electronic structure calculation, X-ray diffraction, small-angle neutron scattering, atomic force microscopy and optical images. The role of hydrogen bonding has been revealed for this type of supramolecular assembly, and in the presence of organically modified nanoclay hydrogen bonding contributes to the formation of bigger clusters of nanocomposites. Controlled biodegradation of PU and its nanocomposites has been investigated in enzymatic media. Biocompatibility of these novel nanocomposites has been extensively verified through platelet adhesion, aggregation and hemolysis assay. Sustained drug delivery by biocompatible pristine PU and its nanocomposites has been demonstrated either by controlling the crystallite size of the polyurethane through alteration of the aliphatic chain length of the extender or by incorporating disc-like nanoclay, creating a tortuous path that results in delayed diffusion. Hence, the developed nanohybrids are potential biomaterials for tissue engineering and drug delivery. PMID:24374322

  13. Mechanisms and modeling of halogenated aliphatic contaminant adsorption by carbon nanotubes.

    PubMed

    Apul, Onur Guven; Zhou, Yang; Karanfil, Tanju

    2015-09-15

    This paper examines the adsorption of environmentally relevant halogenated aliphatic compounds using single-walled (SWCNT) and multi-walled carbon nanotubes (MWCNT), and the development of linear solvation-energy relationships (LSER) to examine those adsorption mechanisms. The poly-parameter LSER model was also compared to those previously generated for the adsorption of aromatic compounds by CNTs. The adsorption affinity of aliphatic compounds was greater on the SWCNT than MWCNT with similar oxygen contents. This was attributed to the pore-filling mechanism that was enhanced by higher micropore volume of the SWCNT bundles over the MWCNT bundles. LSER models showed that, at higher concentrations, B (the hydrogen bond accepting ability) was the most influential descriptor for both SWCNT and MWCNT. Other important descriptors were V followed by P, both of which exhibited a positive correlation with adsorption, indicating that their size and polarizability favors adsorption. The contribution of these descriptors to overall adsorption was 2-3 times less than the B. In comparison, V was the most important descriptor in the aromatic compound LSER models. This difference indicates that adsorbate hydrophobicity greatly affects the adsorption of aromatic compounds by CNTs, whereas, aliphatic compounds are affected by both the hydrophobic driving force and other interactions.

  14. A molecular model for H(2) interactions in aliphatic and aromatic hydrocarbons.

    PubMed

    Figueroa-Gerstenmaier, Susana; Giudice, Simona; Cavallo, Luigi; Milano, Giuseppe

    2009-05-28

    A model for molecular hydrogen interacting with aliphatic and aromatic hydrocarbons is presented. The model has been derived using ab initio techniques and molecular dynamics simulations. In particular, quadrupole moments of hydrogen, and variation on energy with intermolecular distance of different conformations for the hydrogen-benzene couple were calculated using the Møller-Plesset method. Hydrogen was modelled using a two-centre Lennard-Jones potential plus electrostatic interactions. Lennard-Jones parameters were optimized on the basis of a correct reproduction of experimental data of hydrogen solubility in benzene and cyclohexane, calculated using the test particle insertion method. Different sets of parameters for specific interactions (hydrogen-aliphatic and hydrogen-aromatic systems) were considered avoiding the simple use of Lorentz-Berthelot combining rules. Additionally, structural and thermodynamic properties of hydrogen-benzene, hydrogen-cyclohexane and hydrogen in an equimolar mixture of benzene-cyclohexane at different low concentrations of hydrogen were investigated by means of molecular dynamics simulations. Electrostatic charges were taken from ab initio quantum mechanical calculations but after careful analysis of the calculated properties, their irrelevance was evidenced. Moreover, Coulombic interactions make simulations more expensive and, therefore, we do not recommend their inclusion in the modelling of hydrogen-aliphatic and aromatic interactions. PMID:19440622

  15. Exploring mild enzymatic sustainable routes for the synthesis of bio-degradable aromatic-aliphatic oligoesters.

    PubMed

    Pellis, Alessandro; Guarneri, Alice; Brandauer, Martin; Acero, Enrique Herrero; Peerlings, Henricus; Gardossi, Lucia; Guebitz, Georg M

    2016-05-01

    The application of Candida antarctica lipase B in enzyme-catalyzed synthesis of aromatic-aliphatic oligoesters is here reported. The aim of the present study is to systematically investigate the most favorable conditions for the enzyme catalyzed synthesis of aromatic-aliphatic oligomers using commercially available monomers. Reaction conditions and enzyme selectivity for polymerization of various commercially available monomers were considered using different inactivated/activated aromatic monomers combined with linear polyols ranging from C2 to C12 . The effect of various reaction solvents in enzymatic polymerization was assessed and toluene allowed to achieve the highest conversions for the reaction of dimethyl isophthalate with 1,4-butanediol and with 1,10-decanediol (88 and 87% monomer conversion respectively). Mw as high as 1512 Da was obtained from the reaction of dimethyl isophthalate with 1,10-decanediol. The obtained oligomers have potential applications as raw materials in personal and home care formulations, for the production of aliphatic-aromatic block co-polymers or can be further functionalized with various moieties for a subsequent photo- or radical polymerization.

  16. Structure-water solubility modeling of aliphatic alcohols using the weighted path numbers.

    PubMed

    Amić, D; Basak, S C; Lucić, B; Nikolić, S; Trinajstić, N

    2002-03-01

    The structure-water solubility modeling of aliphatic alcohols was performed using the weighted path numbers. Aliphatic alcohols were represented by weighted trees. The weight of the edge representing C-O bond was taken to be x, while the weights of C-C bonds were taken to be all equal to one. Four (one-, two-, three- and four-descriptor) models with weighted path numbers were considered. They were compared with models based on surface areas of aliphatic alcohols, models based on the vertex-connectivity indices for the corresponding alkanes, models based on orthogonal valence vertex-connectivity indices, models based on valence vertex- and edge-connectivity indices with optimum exponents and models based on weighted line graphs. The main result of this comparative study is that the models based on two, three, or four weighted path numbers posses the best statistical characteristics of all models considered in this paper. In addition, the predictive performance of these models was also tested using the training/test set partition. Very good and stable predictions for 19 test set compounds were obtained. For this data set we find, in all performed tests of models, that optimum x values are in the range 3.0-4.0. This result supports views about the potential of the weighted path numbers for deriving high quality structure-property models.

  17. Highly accelerated inverse electron-demand cycloaddition of electron-deficient azides with aliphatic cyclooctynes.

    PubMed

    Dommerholt, Jan; van Rooijen, Olivia; Borrmann, Annika; Guerra, Célia Fonseca; Bickelhaupt, F Matthias; van Delft, Floris L

    2014-01-01

    Strain-promoted azide-alkyne cycloaddition (SPAAC) as a conjugation tool has found broad application in material sciences, chemical biology and even in vivo use. However, despite tremendous effort, SPAAC remains fairly slow (0.2-0.5 M(-1) s(-1)) and efforts to increase reaction rates by tailoring of cyclooctyne structure have suffered from a poor trade-off between cyclooctyne reactivity and stability. We here wish to report tremendous acceleration of strain-promoted cycloaddition of an aliphatic cyclooctyne (bicyclo[6.1.0]non-4-yne, BCN) with electron-deficient aryl azides, with reaction rate constants reaching 2.0-2.9 M(-1) s(-1). A remarkable difference in rate constants of aliphatic cyclooctynes versus benzoannulated cyclooctynes is noted, enabling a next level of orthogonality by a judicious choice of azide-cyclooctyne combinations, which is inter alia applied in one-pot three-component protein labelling. The pivotal role of azide electronegativity is explained by density-functional theory calculations and electronic-structure analyses, which indicates an inverse electron-demand mechanism is operative with an aliphatic cyclooctyne. PMID:25382411

  18. New synthetic aliphatic sulfonamido-quaternary ammonium salts as anticancer chemotherapeutic agents.

    PubMed

    Song, Doona; Yang, Jee Sun; Oh, Changmok; Cui, Shuolin; Kim, Bo-Kyung; Won, Misun; Lee, Jang-ik; Kim, Hwan Mook; Han, Gyoonhee

    2013-11-01

    RhoB is expressed during tumor cell proliferation, survival, invasion, and metastasis. In malignant progression, the expression levels of RhoB are commonly attenuated. RhoB is known to be linked to the regulation of the PI3K/Akt survival pathways. Based on aliphatic amido-quaternary ammonium salts that induce apoptosis via up-regulation of RhoB, we synthesized novel aliphatic sulfonamido-quaternary ammonium salts. These new synthetic compounds were evaluated for their biological activities using an in vitro RhoB promoter assay in HeLa cells, and in a growth inhibition assay using human cancer cell lines including PC-3, NUGC-3, MDA-MB-231, ACHN, HCT-15, and NCI-H23. Compound 5b (ethyl-dimethyl-{3-[methyl-(tetradecane-1-sulfonyl)-amino]-propyl}-ammonium; iodide) was the most promising anticancer agent in the series, based upon the potency of growth inhibition and RhoB promotion. These new aliphatic sulfonamido-quaternary ammonium salts could be a valuable series for development of new anticancer chemotherapeutic agents. PMID:24095759

  19. Exploring mild enzymatic sustainable routes for the synthesis of bio-degradable aromatic-aliphatic oligoesters.

    PubMed

    Pellis, Alessandro; Guarneri, Alice; Brandauer, Martin; Acero, Enrique Herrero; Peerlings, Henricus; Gardossi, Lucia; Guebitz, Georg M

    2016-05-01

    The application of Candida antarctica lipase B in enzyme-catalyzed synthesis of aromatic-aliphatic oligoesters is here reported. The aim of the present study is to systematically investigate the most favorable conditions for the enzyme catalyzed synthesis of aromatic-aliphatic oligomers using commercially available monomers. Reaction conditions and enzyme selectivity for polymerization of various commercially available monomers were considered using different inactivated/activated aromatic monomers combined with linear polyols ranging from C2 to C12 . The effect of various reaction solvents in enzymatic polymerization was assessed and toluene allowed to achieve the highest conversions for the reaction of dimethyl isophthalate with 1,4-butanediol and with 1,10-decanediol (88 and 87% monomer conversion respectively). Mw as high as 1512 Da was obtained from the reaction of dimethyl isophthalate with 1,10-decanediol. The obtained oligomers have potential applications as raw materials in personal and home care formulations, for the production of aliphatic-aromatic block co-polymers or can be further functionalized with various moieties for a subsequent photo- or radical polymerization. PMID:26762794

  20. The influence of chemical composition of aliphatic-aromatic copolyesters on their properties

    SciTech Connect

    Wojtczak, Malgorzata; Galeski, Andrzej; Piorkowska, Ewa; Dutkiewicz, Slawomir

    2014-05-15

    The chain microstructure and properties of a series of aliphatic-aromatic copolyesters in a range of compositions from 10 to 100% of aromatic components were studied by examining melting and crystallization behaviors, dynamic mechanical response, morphology, wide- (WAXS) and small-angle X-ray scattering (SAXS), and tensile deformation. Chain microstructure was analyzed by {sup 1}H NMR. The results indicate that most of copolyesters used in this study have essentially random distribution of comonomers. Copolyesters with more than 30 mol% of aromatic part crystallize with a crystal structure characteristic for homopolymer poly(butylene terephthalate) (PBT). However, some of the reflections from crystal planes are shifted towards lower diffraction angles as compared to butylene terephthalate homoplymer. The phase transition temperatures decrease with increasing aliphatic content. By means of polarized light microscopy (PLM), small-angle light scattering (SALS) and SAXS, crystallization behavior of a selected aliphatic-aromatic copolyester was further explored. Selected copolyester crystallizes in the form of thin fibrous crystals, few nanometers thick, which is the main factor influencing the depression of its melting temperature.

  1. Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

    PubMed

    Jesus, João; Frascari, Dario; Pozdniakova, Tatiana; Danko, Anthony S

    2016-05-15

    This review analyses kinetic studies of aerobic cometabolism (AC) of halogenated aliphatic hydrocarbons (HAHs) from 2001-2015 in order to (i) compare the different kinetic models proposed, (ii) analyse the estimated model parameters with a focus on novel HAHs and the identification of general trends, and (iii) identify further research needs. The results of this analysis show that aerobic cometabolism can degrade a wide range of HAHs, including HAHs that were not previously tested such as chlorinated propanes, highly chlorinated ethanes and brominated methanes and ethanes. The degree of chlorine mineralization was very high for the chlorinated HAHs. Bromine mineralization was not determined for studies with brominated aliphatics. The examined research period led to the identification of novel growth substrates of potentially high interest. Decreasing performance of aerobic cometabolism were found with increasing chlorination, indicating the high potential of aerobic cometabolism in the presence of medium- and low-halogenated HAHs. Further research is needed for the AC of brominated aliphatic hydrocarbons, the potential for biofilm aerobic cometabolism processes, HAH-HAH mutual inhibition and the identification of the enzymes responsible for each aerobic cometabolism process. Lastly, some indications for a possible standardization of future kinetic studies of HAH aerobic cometabolism are provided. PMID:26874310

  2. The influence of chemical composition of aliphatic-aromatic copolyesters on their properties

    NASA Astrophysics Data System (ADS)

    Wojtczak, Malgorzata; Galeski, Andrzej; Dutkiewicz, Slawomir; Piorkowska, Ewa

    2014-05-01

    The chain microstructure and properties of a series of aliphatic-aromatic copolyesters in a range of compositions from 10 to 100% of aromatic components were studied by examining melting and crystallization behaviors, dynamic mechanical response, morphology, wide- (WAXS) and small-angle X-ray scattering (SAXS), and tensile deformation. Chain microstructure was analyzed by 1H NMR. The results indicate that most of copolyesters used in this study have essentially random distribution of comonomers. Copolyesters with more than 30 mol% of aromatic part crystallize with a crystal structure characteristic for homopolymer poly(butylene terephthalate) (PBT). However, some of the reflections from crystal planes are shifted towards lower diffraction angles as compared to butylene terephthalate homoplymer. The phase transition temperatures decrease with increasing aliphatic content. By means of polarized light microscopy (PLM), small-angle light scattering (SALS) and SAXS, crystallization behavior of a selected aliphatic-aromatic copolyester was further explored. Selected copolyester crystallizes in the form of thin fibrous crystals, few nanometers thick, which is the main factor influencing the depression of its melting temperature.

  3. Development of low cost pulmonary surfactants composed of a mixture of lipids or lipids-peptides using higher aliphatic alcohol or soy lecithin.

    PubMed

    Yukitake, Ko; Nakamura, Yoshihiro; Kawahara, Masato; Nakahara, Hiromichi; Shibata, Osamu; Lee, Sannamu

    2008-10-15

    The artificial pulmonary surfactant composition in the present study is characterized by a lipid mixture system composed of higher aliphatic alcohol, egg yolk phosphatidylcholine (egg PC), soy lecithin and higher aliphatic acid as the major components or a peptide-lipid mixture system composed of a combination of the lipid mixture system to which a peptide is added. Three peptides with amphiphilic surface-staying, membrane spanning, and both properties were designed and synthesized. The evaluation of pulmonary surfactant assay was performed by a hysteresis curve drawn upon the measurement for the surface tension-area curve with the Wilhelmy surface tensometer in vitro and the recovery of lung compliance for the pulmonary surfactant-deficient rat models in vivo. Lipid-mixture systems composed of octadecanol or soy lecithins containing no peptide were favorable hysteresis curves as compared with commercially available Surfacten, but were not prominent. The peptide-lipid mixture systems composed of a combination of the lipid mixture of alkyl alcohol or soy lecithin to which peptides designed were added were desirable hysteresis curves similar to Surfacten and amphiphilic Hel 13-5 peptide-lipids mixture systems were much more effective than the lipid mixture system. Particularly, the recovery of lung compliance treated with hydrogenated soy lecithin-fractionated soy lecithin PC70-palmitic acid-peptide Hel 13-5 (40:40:17.5:2.5, w/w) was comparable to that with Surfacten. Because the artificial pulmonary surfactant compositions of this study can be prepared at lower costs, they are useful for the treatment of respiratory distress syndrome and acute respiratory distress syndrome as well as for inflammatory pulmonary diseases, dyspnea caused by asthma, etc.

  4. Organic acids in continental background aerosols

    NASA Astrophysics Data System (ADS)

    Limbeck, Andreas; Puxbaum, Hans

    With a newly developed method aerosol samples from three distinctly different continental sites were analyzed: an urban site (Vienna), a savanna site in South Africa (Nylsvley Nature Reserve, NNR) and a free tropospheric continental background site (Sonnblick Observatory, SBO). In all samples a range of monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) has been identified and quantified. The three most abundant MCAs in Vienna were the C18, C16 and C14 acids with concentrations of 66, 45 and 36 ng m -3, respectively. At the mid tropospheric background site (SBO) the three most abundant MCAs were the C18, C16 and C12 acid. For the DCAs at all three sites oxalic, malonic and succinic acid were the dominant compounds. For some individual compounds an information about the sources could be obtained. For example the determined unsaturated MCAs in South Africa appear to result from biogenic sources whereas in Vienna those acids are considered to be derived from combustion processes. Oxalic and glyoxalic acid appear to have a free tropospheric air chemical source. The relative high amounts at SBO in comparison to Vienna can only be explained by secondary formation of oxalic acid in the atmosphere.

  5. Scavenging of SO 4- radical anions by mono- and dicarboxylic acids in the Mn(II)-catalyzed S(IV) oxidation in aqueous solution

    NASA Astrophysics Data System (ADS)

    Grgić, Irena; Podkrajšek, Boštjan; Barzaghi, Paolo; Herrmann, Hartmut

    The rate constants for reactions of the SO 4- radical anion with some low molecular weight monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) and their anions using the laser flash photolysis-long path laser absorption (LFP-LPLA) technique were determined. The present study contains the first measured rate constants for SO 4- reactions with glycolic, lactic, malic and malonic acid. The rate constants are found to be in the range from 10 5 to 10 7 M -1 s -1, with the lower values found for acids and higher values for their respective anions. In addition, the rate constants for scavenging of SO 4- by all investigated organics in the Mn(II)-catalyzed S(IV) autoxidation at pH 4.5 and T=25 °C were determined by means of the reversed rate method. The comparison between these rate constants and the rate constants obtained by direct measurements confirms the proposed inhibiting mechanism for the Mn(II)-catalyzed S(IV) autoxidation in the presence of monocarboxylic acids. In the case of formic acid, which causes the highest inhibition, this mechanism can explain the second part of kinetic traces (i.e. after the induction period). Surprisingly, although dicarboxylic acids are reactive toward SO 4- they do not contribute to the inhibition of S(IV) oxidation (especially malic and malonic acids).

  6. Direct Ruthenium-Catalyzed Hydrogenation of Carboxylic Acids to Alcohols.

    PubMed

    Cui, Xinjiang; Li, Yuehui; Topf, Christoph; Junge, Kathrin; Beller, Matthias

    2015-09-01

    The "green" reduction of carboxylic acids to alcohols is a challenging task in organic chemistry. Herein, we describe a general protocol for generation of alcohols by catalytic hydrogenation of carboxylic acids. Key to success is the use of a combination of Ru(acac)3, triphos and Lewis acids. The novel method showed broad substrate tolerance and a variety of aliphatic carboxylic acids including biomass-derived compounds can be smoothly reduced.

  7. In vitro studies of degradation and bioactivity of aliphatic polyester composites

    NASA Astrophysics Data System (ADS)

    Chouzouri, Georgia

    In spite of numerous publications on the potential use of combinations of aliphatic polyester composites containing bioactive fillers for bone regeneration, little information exists on the combined in vitro mechanisms involving simultaneously diffusion for polymer degradation and bioactivity through nucleation and growth of apatite in simulated body fluid (SBF) solution. The objective of this study is to contribute to the understanding of the fundamentals in designing non-porous, solid materials for bone regeneration, from experimental data along with their engineering interpretation. Bioactivity, in terms of apatite growth, was assessed through several experimental methods such as scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray-diffraction (XRD) and changes in ion concentration. In the case of the six neat fillers evaluated, the filler shape, form and chemical structure showed significant differences in bioactivity response. Bioglass and calcium silicate fillers showed faster nucleation and growth rates in the screening experiments. Composites at 30% by weight filler were prepared by solution and/or melt mixing. Polycaprolactone (PCL) composites containing five different fillers were evaluated. Solution processed PCL/calcium silicate (CS) samples showed faster bioactivity, as determined by apatite growth, compared to melt mixed samples. The onset time for bioactivity was different for all PCL composites. The limited bioactivity in the PCL composites over longer periods of time could be attributed to the PCL hydrophobicity leading to a slow polymer degradation rate, and also to the lack of SBF replenishment. For both polylactic acid (PLA) composites containing CS and bioglass, significant growth was observed after one week and in the case of CS was still evident after four weeks immersion. However, at prolonged time periods no further bioactivity was observed, although ion release results indicated a faster release rate that would

  8. Homoeologous GSL-ELONG gene replacement for manipulation of aliphatic glucosinolates in Brassica rapa L. by marker assisted selection.

    PubMed

    Hirani, Arvind H; Zelmer, Carla D; McVetty, Peter B E; Daayf, Fouad; Li, Genyi

    2013-01-01

    Aliphatic glucosinolates are the predominant sulfur-rich plant secondary metabolites in economically important Brassica crops. Glucosinolates and their hydrolysis products are involved in plant-microbe, plant-insect, plant-animal, and plant-human interactions. It is, therefore, important to manipulate glucosinolate profiles and contents in Brassica species. In this study, aliphatic glucosinolates were genetically manipulated through homoeologous recombination in backcross lines followed by marker assisted selection in B. rapa. A resynthesized B. napus line, from a cross between B. rapa and B. oleracea, was backcrossed with Chinese cabbage doubled haploid line, RI16. Marker assisted selection for non-functional gene was performed in each backcross generations. Advanced backcross progenies (BC3F2) were developed to identify homoeologous gene replacement and/or introgression. Reduction in 5C aliphatic glucosinolates (gluconapoleiferin, glucoalyssin, and glucobrassicanapin) was observed in BC3F2 progenies of the recurrent parent that carried the GSL-ELONG (-) gene. The GSL-ELONG (-) positive backcross progenies were also screened by the A-genome and BraGSL-ELONG gene specific marker, which linked with 5C aliphatic glucosinolates. The A-genome specific marker was absent in the plants of advanced backcross progenies which showed reduction in 5C aliphatic glucosinolates. The results suggest that the functional allele had been replaced by the non-functional GSL-ELONG (-) allele from B. oleracea. Some advanced backcross progenies (BC3F2) positive for the GSL-ELONG (-) allele and the A-genome specific SCAR marker BraMAM1-1 did not show reduction in 5C aliphatic glucosinolates, suggesting that GSL-ELONG (-) allele is recessive. Replacement of the functional locus in the A-genome by non-functional counterpart in the C-genome reduced the content of 5C aliphatic glucosinolates in B. rapa seeds with 20 μmol/g.

  9. Homoeologous GSL-ELONG gene replacement for manipulation of aliphatic glucosinolates in Brassica rapa L. by marker assisted selection

    PubMed Central

    Hirani, Arvind H.; Zelmer, Carla D.; McVetty, Peter B. E.; Daayf, Fouad; Li, Genyi

    2013-01-01

    Aliphatic glucosinolates are the predominant sulfur-rich plant secondary metabolites in economically important Brassica crops. Glucosinolates and their hydrolysis products are involved in plant–microbe, plant–insect, plant–animal, and plant–human interactions. It is, therefore, important to manipulate glucosinolate profiles and contents in Brassica species. In this study, aliphatic glucosinolates were genetically manipulated through homoeologous recombination in backcross lines followed by marker assisted selection in B. rapa. A resynthesized B. napus line, from a cross between B. rapa and B. oleracea, was backcrossed with Chinese cabbage doubled haploid line, RI16. Marker assisted selection for non-functional gene was performed in each backcross generations. Advanced backcross progenies (BC3F2) were developed to identify homoeologous gene replacement and/or introgression. Reduction in 5C aliphatic glucosinolates (gluconapoleiferin, glucoalyssin, and glucobrassicanapin) was observed in BC3F2 progenies of the recurrent parent that carried the GSL-ELONG- gene. The GSL-ELONG- positive backcross progenies were also screened by the A-genome and BraGSL-ELONG gene specific marker, which linked with 5C aliphatic glucosinolates. The A-genome specific marker was absent in the plants of advanced backcross progenies which showed reduction in 5C aliphatic glucosinolates. The results suggest that the functional allele had been replaced by the non-functional GSL-ELONG- allele from B. oleracea. Some advanced backcross progenies (BC3F2) positive for the GSL-ELONG- allele and the A-genome specific SCAR marker BraMAM1-1 did not show reduction in 5C aliphatic glucosinolates, suggesting that GSL-ELONG- allele is recessive. Replacement of the functional locus in the A-genome by non-functional counterpart in the C-genome reduced the content of 5C aliphatic glucosinolates in B. rapa seeds with 20 μmol/g. PMID:23532458

  10. Identification of diamino acids in the Murchison meteorite

    NASA Astrophysics Data System (ADS)

    Meierhenrich, Uwe J.; Muñoz Caro, Guillermo M.; Hendrik Bredehöft, Jan; Jessberger, Elmar K.; Thiemann, Wolfram H.-P.

    Amino acids identified in the Murchison chondritic meteorite by molecular and isotopic analysis are thought to have been delivered to the early Earth by asteroids, comets, and interplanetary dust particles where they may have triggered the appearance of life by assisting in the synthesis of proteins via prebiotic polycondensation reactions [Oró, J. (1961) Nature 190, 389-390; Chyba, C. F. & Sagan, C. (1992) Nature 355, 125-132]. We report the identification of diamino acids in the Murchison meteorite by new enantioselective GC-MS analyses. DL-2,3-diaminopropanoic acid, DL-2,4-diaminobutanoic acid, 4,4'-diaminoisopentanoic acid, 3,3'-diaminoisobutanoic acid, and 2,3-diaminobutanoic acid were detected in the parts per billion range after chemical transformation into N,N-diethoxycarbonyl ethyl ester derivatives. The chiral diamino acids show a racemic ratio. Laboratory data indicate that diamino acids support the formation of polypeptide structures under primitive Earth conditions [Brack, A. & Orgel, L. E. (1975) Nature 256, 383-387] and suggest polycondensation reactions of diamino acids into early peptide nucleic acid material as one feasible pathway for the prebiotic evolution of DNA and RNA genomes [Joyce, G. F. (2002) Nature 418, 214-221]. The results obtained in this study favor the assumption that not only amino acids (as the required monomers of proteins) form in interstellar/circumstellar environments, but also the family of diamino monocarboxylic acids, which might have been relevant in prebiotic chemistry.

  11. Dicarboxylic acids with limited numbers of hydrocarbons stabilize cell membrane and increase osmotic resistance in rat erythrocytes.

    PubMed

    Mineo, Hitoshi; Amita, Nozomi; Kawawake, Megumi; Higuchi, Ayaka

    2013-11-01

    We examined the effect of dicarboxylic acids having 0 to 6 hydrocarbons and their corresponding monocarboxylic or tricarboxylic acids in changing the osmotic fragility (OF) in rat red blood cells (RBCs). Malonic, succinic, glutaric and adipic acids, which are dicarboxylic acids with 1, 2, 3 and 4 straight hydrocarbons located between two carboxylic groups, decreased the OF in a concentration-dependent manner. Other long-chain dicarboxylic acids did not change the OF in rat RBCs. The benzoic acid derivatives, isophthalic and terephthalic acids, but not phthalic acid, decreased the OF in a concentration-dependent manner. Benzene-1,2,3-tricarboxylic acid, but not benzene-1,3,5-tricarboxylic acid, also decreased the OF in rat RBCs. On the other hand, monocarboxylic acids possessing 2 to 7 straight hydrocarbons and benzoic acid increased the OF in rat RBCs. In short-chain dicarboxylic acids, a limited number of hydrocarbons between the two carboxylic groups are thought to form a V- or U-shaped structure and interact with phospholipids in the RBC membrane. In benzene dicarboxylic and tricarboxylic acids, a part of benzene nucleus between the two carboxylic groups is thought to enter the plasma membrane and act on acyl-chain in phospholipids in the RBC membrane. For dicarboxylic and tricarboxylic acids, limited numbers of hydrocarbons in molecules are speculated to enter the RBC membrane with the hydrophilic carboxylic groups remaining outside, stabilizing the structure of the cell membrane and resulting in an increase in osmotic resistance in rat RBCs. PMID:23770357

  12. The Galactic Distribution of Aliphatic Hydrocarbons in the Diffuse Interstellar Medium

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Pendleton, Yvonne J.; Allamandola, Louis J.

    1995-01-01

    The infrared absorption feature near 2950/ cm (3.4 microns), characteristic of dust in the diffuse interstellar medium (ISM), is attributed to C-H stretching vibrations of aliphatic hydrocarbons. We show here that the strength of the band does not scale linearly with visual extinction everywhere, but instead increases more rapidly for objects near the center of the Galaxy, a behavior that parallels that of the Si-O stretching band due to silicate materials in the diffuse ISM. This implies that the grains responsible for the diffuse medium aliphatic C-H and silicate Si-O stretching bands are different from those responsible for much of the observed visual extinction. It also suggests that the distribution of the carbonaceous component of the diffuse ISM is not uniform throughout the Galaxy, but instead may increase in density toward the center of the Galaxy. The similar behavior of the C-H and Si-O stretching bands suggests that these two components may be coupled, perhaps in the form of silicate-core, organic-mantle grains. Several possible models of the distribution of this material are presented and it is demonstrated that the inner parts of the Galaxy has a carrier density that is 5 to 35 times higher than in the local ISM. Depending on the model used, the density of aliphatic material in the local ISM is found to be about 1 to 2 -CH3 groups /cc and about 2 to 5 -CH2- groups/cc. These densities are consistent with the strengths of the 2955 and 2925/ cm (3.38 and 3.42 microns) subfeatures (due to -CH3 and -CH2- groups, respectively) within the overall 2950/ cm (3.4 microns) band being described by the relations A(sub upsilon)/tau(sub 2925/cm) = 270 +/- 40 and A(sub upsilon)/tau(sub 2925/cm) = 250 +/- 40 in the local diffuse ISM.

  13. The galactic distribution of aliphatic hydrocarbons in the diffuse interstellar medium

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Pendleton, Yvonne J.; Allamandola, Louis J.

    1995-01-01

    The infrared absorption feature near 2950(exp -1) (3.4 micron), characteristic of dust in the diffuse interstellar medium (ISM), is attributed to C-H stretching vibrations of aliphatic hydrocarbons. We show here that the strength of the band does not scale linearly with visual extinction everywhere, but instead increases more rapidly for objects near the center of the Galaxy, a behavior that parallels that of the Si-O stretching band due to silicate materials in the diffuse ISM. This implies that the grains responsible for the diffuse medium aliphatic C-H and silicate Si-O stretching bands are different from those responsible for much of the observed visual extinction. It also suggests that the distribution of the carbonaceous component of the diffuse ISM is not uniform throughout the Galaxy, but instead may increase in density toward the center of the Galaxy. The similar behavior of the C-H and Si-O stretching bands suggests that these two components may be coupled, perhaps in the form of silicate-core, organic-mantle grains. Several possible models of the distribution of this material are presented and it is demonstrated that the inner parts of the Galaxy has a carrier density that is 5 to 35 times higher than in the local ISM. Depending on the model used, the density of aliphatic material in the local ISM is found to be about 1 to 2 -CH3 groups m(exp -3) and about 2 to 5 -CH2- groups m(exp -3). These densities are consistent with the strengths of the 2955 and 2925 cm(exp -1) (3.4 micron) band being described by the relations A(sub nu)/tau(sub 2955 cm(exp -1)) = 270 +/- 40 and A(sub nu)/tau(sub 2925 cm(exp -1)) = 250 +/- 40 in the local diffuse ISM.

  14. Reduction of amphetamine hydroxylamine and other aliphatic hydroxylamines by benzamidoxime reductase and human liver microsomes.

    PubMed

    Clement, B; Behrens, D; Möller, W; Cashman, J R

    2000-10-01

    For the reduction of N-hydroxylated derivatives of strongly basic functional groups, such as amidines, guanidines, and aminohydrazones, an oxygen-insensitive liver microsomal system, the benzamidoxime reductase, has been described. To reconstitute the complete activity of the benzamidoxime reductase, the system required cytochrome b(5), NADH-cytochrome b(5)-reductase, and the benzamidoxime reductase, a cytochrome P450 enzyme, which has been purified to homogeneity from pig liver. It was not known if this enzyme system was also capable of reducing aliphatic hydroxylamines. The N-hydroxylation of aliphatic amines is a well-known metabolic process. It was of interest to study the possibility of benzamidoxime reductase reducing N-hydroxylated metabolites of aliphatic amines back to the parent compound. Overall, N-hydroxylation and reduction would constitute a futile metabolic cycle. As examples of medicinally relevant compounds, the hydroxylamines of methamphetamine, amphetamine, and N-methylamine as model compounds were investigated. Formation of methamphetamine and amphetamine was analyzed by newly developed HPLC methods. All three hydroxylamines were easily reduced by benzamidoxime reductase to their parent amines with reduction rates of 220.6 nmol min(-1) (mg of protein)(-1) for methamphetamine, 5.25 nmol min(-1) (mg of protein)(-1) for amphetamine, and 153 nmol min(-1) (mg of protein)(-1) for N-methylhydroxylamine. Administration of synthetic hydroxylamines of amphetamine and methamphetamine to primary rat neuronal cultures produced frank cell toxicity. Compared with amphetamine or the oxime of amphetamine, the hydroxylamines were significantly more toxic to primary neuronal cells. The benzamidoxime reductase is therefore involved in the detoxication of these reactive hydroxylamines.

  15. Potential Alternatives Report for Validation of Alternatives to Aliphatic Isocyanate Polyurethanes

    NASA Technical Reports Server (NTRS)

    Lewis, pattie

    2011-01-01

    Identifying and selecting alternative materials and technologies that have the potential to reduce the identified HazMats and hazardous air pollutants (HAPs), while incorporating sound corrosion prevention and control technologies, is a complicated task due to the fast pace at which new technologies emerge and rules change. The alternatives are identified through literature searches, electronic database and Internet searches, surveys, and/or personal and professional contacts. Available test data was then compiled on the proposed alternatives to determine if the materials meet the test objectives or if further)laboratory or field-testing will be required. After reviewing technical information documented in the PAR, government representatives, technical representatives from the affected facilities, and other stakeholders involved in the process will select the list of viable alternative coatings for consideration and testing under the project's Joint Test Protocol entitled Joint Test Protocol for Validation of Alternatives to Aliphatic Isocyanate Polyurethanes and Field Test Plan entitled Field Evaluations Test Plan for Validation of Alternatives to Aliphatic Isocyanate Polyurethanes, both prepared by ITB. Test results will be reported in a Joint Test Report upon completion oftesting. The selection rationale and conclusions are documented in this PAR. A cost benefit analysis will be prepared to quantify the estimated capital and process costs of coating alternatives and cost savings relative to the current coating processes, however, some initial cost data has been included in this PAR. For this coatings project, isocyanates, as found in aliphatic isocyanate polyurethanes, were identified as the target HazMat to be eliminated. Table 1-1 lists the target HazMats, the related process and application, current specifications, and affected programs.

  16. Methyl oleate deoxygenation for production of diesel fuel aliphatic hydrocarbons over Pd/SBA-15 catalysts

    PubMed Central

    2013-01-01

    Background Catalytic deoxygenation is a prominent process for production of renewable fuels from vegetable oil. In this work, deoxygenation of technical grade methyl oleate to diesel fuel aliphatic hydrocarbons (C15 – C18) is evaluated with several parameters including temperature, hydrogen pressure and reaction time in a stirred batch reactor over Pd/SBA-15 catalysts. Results Two different SBA-15 morphologies i.e. spherelike and necklacelike structures have been synthesize as supports for Pd active metal. It is found that Pd dispersion on necklacelike SBA-15 is higher than that of spherelike SBA-15. Notably, higher Pd dispersion on necklacelike SBA-15 provides significant deoxygenation efficiency as compared to Pd/SBA-15-spherelike. Results show that H2 pressures greatly determine the total ester conversion and selectivity to C15 – C18 aliphatic hydrocarbons. Total ester conversions with 55< selectivity to n-heptadecane are achieved using Pd/SBA-15-necklacelike at 270°C and 60 bar H2 pressure within 6 h reaction time. Gas phase study reveals that formation of C17 is generated via indirect decarbonylation when the reaction time is prolonged. Conclusions Pd/SBA-15-necklacelike catalyst exhibits good catalytic performance with high selectivity to diesellike aliphatic hydrocarbons (C15 – C18). The physicochemical properties of the Pd supported on different SBA-15 morphologies influence the deoxygenation activity of the catalysts. Furthermore, the reaction pathways are governed by the H2 pressure as well as reaction duration. PMID:24011181

  17. The fumigant and repellent activity of aliphatic lactones against Pediculus humanus capitis (Anoplura: Pediculidae).

    PubMed

    Toloza, Ariel Ceferino; Zygadlo, Julio; Mougabure-Cueto, Gastón; Zerba, Eduardo; Faillaci, Silvina; Picollo, María Inés

    2006-02-01

    New alternative insecticides are necessary for the chemical control of head lice. In this study the fumigant knockdown time 50% (KT50) and repellency index (RI) of three aliphatic lactones was compared with two essential oils and DDVP, against permethrin-resistance Pediculus humanus capitis from Argentina. In the fumigant assay, none of the lactones were effective compared to the highest activity of eucalyptus (KT50 15.53 m). In the repellency test, the three lactones were equally or more effective (RI ranging from 60.50 to 76.68) than the positive control (piperonal). These lactones are promising as head lice repellents. PMID:16699710

  18. Electrooxidation of aliphatic alcohols on electrodes consisting of hydrophobicized supports coated with nickel oxides

    SciTech Connect

    Chaenko, N.V.; Kornienko, V.L.; Avrutskaya, I.A.; Fioshin, M.Ya.

    1987-12-01

    Two methods are presented to intensify the electrooxidation of aliphatic alcohols with low water solubility and to simplify end-product separation. One method comprised direct addition of higher nickel oxides to the active material of the electrode to be fabricated; the other involved depositing a layer of higher nickel oxides on a hydrophobicized support consisting of a mixture of a conducting material and the FP-4D hydrophobicizer. Electrolysis was carried out in a diaphragm-free two-compartment cell, one reagent and the other the electrolyte. Results are shown of hexyl alcohol oxidation on various composition supports coated with higher nickel oxides.

  19. External validation of a QSAR for the acute toxicity of halogenated aliphatic hydrocarbons

    SciTech Connect

    Eriksson, L.; Jonsson, J. . Dept. of Organic Chemistry); Berglind, R. . NBC-Defense Research)

    1993-07-01

    The validation of the predictive capability of a quantitative structure-activity relationship (QSAR) is a significant step toward the construction of a reliable model. This point is discussed and illustrated with data for a class of halogenated aliphatic hydrocarbons. For this class of compounds, a QSAR concerning their acute toxicity toward rate was recently published. This QSAR is verified in this by selecting and testing an external validation set comprising six compounds. The QSAR is also used for predicting the acute toxicity of 28 nontested members of this class.

  20. Brominated aliphatic hydrocarbons and sterols from the sponge Xestospongia testudinaria with their bioactivities.

    PubMed

    Zhou, Xuefeng; Lu, Yanan; Lin, Xiuping; Yang, Bin; Yang, Xianwen; Liu, Yonghong

    2011-10-01

    Four brominated aliphatic hydrocarbons (1-4), including a novel brominated ene-tetrahydrofuran named as mutafuran H (1), and five sterols (5-9) were isolated from the South China Sea sponge Xestospongia testudinaria. The structure of 1 was determined on the basis of NMR ((1)H, (13)C NMR, HSQC, HMBC, (1)H-(1)H COSY, and NOESY), MS, and optical rotation analysis. Known compounds were identified by comparison of their NMR data with those reported in the literature. Compounds 1-4, and 6-9 were evaluated for their toxicity against Artemia salina larvae, and anti-acetylcholinesterase activity.

  1. Process for removing halogenated aliphatic and aromatic compounds from petroleum products. [Polychlorinated biphenyls; methylene chloride; perchloroethylene; trichlorofluoroethane; trichloroethylene; chlorobenzene

    DOEpatents

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1982-03-31

    A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contracting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible polyhydroxy compound, such as, water, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds in the low polar or nonpolar solvent by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered for recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 2 tables.

  2. Aliphatic side chains of proteins as potential geomarkers of NOM liberated from the melting permafrost and discharged to the Arctic Ocean by the Kolyma River run off

    NASA Astrophysics Data System (ADS)

    Dubinenkov, I. V.; Perminova, I.; Kononikhin, A.; Nikolaev, E.; Hertkorn, N.; Bulygina, E. B.; Holmes, R. M.

    2011-12-01

    The Arctic ecosystem is highly sensitive to climate change. Global warming might have considerable effects on regional carbon cycling due to permafrost melting. Permafrost in the Arctic region represents an extremely large organic carbon reservoir mostly stored in the permafrost. Mobilization of just a small portion of carbon stored in Arctic soils will have considerable impacts on the flux of organic carbon from land to the Arctic Ocean, which can affect the Arctic environment. The Kolyma River watershed is one of the Arctic Ocean's largest. It is dominated by continuous permafrost which is underlain with rich organic soils susceptible to increased fluvial transport. The goal of the work was to analyze the structure of isolated natural organic matter from different fresh water environments of the Kolyma river basin. NOM was isolated from the Kolyma River main stream, its tributaries, a thermokarst lake, a floodplain stream and the permafrost. Solid phase extraction technique was used with Bond Elute PPL cartridges. Nuclear magnetic resonance spectroscopy (NMR) and Fourier Transform Ion Cyclotron Resonance Mass Spectroscopy (FTICRMS) was used for structural studies because of unsurpassed molecular level structural information provided by these high resolution magnetic resonance techniques. The NOM samples from the Kolyma River showed high contents of non-substituted aliphatic structures with a low content of aromatics and carbohydrates. Aliphatic nature may indicate a microbial source of NOM in the form of degraded terpenoids and hopanols. It was shown that almost all NOM samples from the rivers had similar molecular composition enriched with aliphatic units. The samples from permafrost mud streams were significantly different and contained sharp peptide signatures. In general, permafrost NOM contained much less degraded peptide residuest as compared to riverine samples. Identification of these residues showed the presence of branched amino acids (valine, alanine

  3. Identification and Synthesis of (Z,Z)-8,11-Heptadecadienyl Formate and (Z)-8-Heptadecenyl Formate: Unsaturated Aliphatic Formates Found in the Unidentified Astigmatid Mite, Sancassania sp. Sasagawa (Acari: Acaridae).

    PubMed

    Shimizu, Nobuhiro; Sakata, Daisuke; Miyazaki, Honami; Shimura, Yasuhiro; Kuwahara, Yasumasa

    2016-01-01

    We identified two aliphatic formates, (Z,Z)-8,11-heptadecadienyl formate and (Z)-8-heptadecenyl formate in the opisthonotal gland secretions of an unidentified acarid species, namely Sancassania sp. Sasagawa. Both compounds were isolated using silica gel column chromatography and the structures were elucidated by ¹H-NMR and GC/FT-IR. Further information on the double bond positions was obtained by GC-MS analysis of the corresponding dimethyl disulfide derivatives. Based on the estimated structures of the two formates and using linoleic and oleic acids as the respective starting materials, a simple four-step synthesis was achieved via Barton decarboxylation as the key step. The aliphatic formates identified in acarids thus far are neryl formate ((Z)-3,7-dimethylocta-2,6-dienyl formate) and lardolure (1,3,5,7-tetramethyldecyl formate), and both have been reported to have pheromone functions. The biological function of the two formates isolated in this study is currently being investigated. Although we can speculate that the two compounds were biosynthesized from linoleic and oleic acid, there is a possibility that the synthetic processes featured a novel chain shortening and formic acid esterification mechanism. PMID:27187322

  4. Tuning reactivity and selectivity in hydrogen atom transfer from aliphatic C-H bonds to alkoxyl radicals: role of structural and medium effects.

    PubMed

    Salamone, Michela; Bietti, Massimo

    2015-11-17

    magnitude. Medium effects on HAT from aliphatic C-H bonds to CumO(•) have been also investigated. With basic substrates, from large to very large decreases in kH have been measured with increasing solvent hydrogen bond donor (HBD) ability or after addition of protic acids or alkali and alkaline earth metal ions, with kinetic effects that exceed 2 orders of magnitude in the reactions of tertiary alkylamines and alkanamides. Solvent hydrogen bonding, protonation, and metal ion binding increase the electron deficiency and the strength of the C-H bonds of these substrates deactivating these bonds toward HAT, with the extent of this deactivation being modulated by varying the nature of the substrate, solvent, protic acid, and metal ion. These results indicate that through these interactions careful control over the HAT reactivity of basic substrates toward CumO(•) and other electrophilic radicals can be achieved, suggesting moreover that these effects can be exploited in an orthogonal fashion for selective C-H bond functionalization of substrates bearing different basic functionalities. PMID:26545103

  5. Tuning reactivity and selectivity in hydrogen atom transfer from aliphatic C-H bonds to alkoxyl radicals: role of structural and medium effects.

    PubMed

    Salamone, Michela; Bietti, Massimo

    2015-11-17

    magnitude. Medium effects on HAT from aliphatic C-H bonds to CumO(•) have been also investigated. With basic substrates, from large to very large decreases in kH have been measured with increasing solvent hydrogen bond donor (HBD) ability or after addition of protic acids or alkali and alkaline earth metal ions, with kinetic effects that exceed 2 orders of magnitude in the reactions of tertiary alkylamines and alkanamides. Solvent hydrogen bonding, protonation, and metal ion binding increase the electron deficiency and the strength of the C-H bonds of these substrates deactivating these bonds toward HAT, with the extent of this deactivation being modulated by varying the nature of the substrate, solvent, protic acid, and metal ion. These results indicate that through these interactions careful control over the HAT reactivity of basic substrates toward CumO(•) and other electrophilic radicals can be achieved, suggesting moreover that these effects can be exploited in an orthogonal fashion for selective C-H bond functionalization of substrates bearing different basic functionalities.

  6. Direct nitration and azidation of aliphatic carbons by an iron-dependent halogenase

    PubMed Central

    Chang, Wei-chen; Layne, Andrew P; Miles, Linde A; Krebs, Carsten

    2014-01-01

    Iron-dependent halogenases employ cis-halo-Fe(IV)-oxo (haloferryl) complexes to functionalize unactivated aliphatic carbon centers, a capability elusive to synthetic chemists. Halogenation requires (1) coordination of a halide anion (Cl− or Br−) to the enzyme's Fe(II) cofactor; (2) coupled activation of O2 and decarboxylation of α-ketoglutarate to generate the haloferryl intermediate; (3) abstraction of hydrogen (H•) from the substrate by the ferryl oxo group; and (4) transfer of the cis halogen as Cl• or Br• to the substrate radical. This enzymatic solution to an unsolved chemical challenge is potentially generalizable to installation of other functional groups, provided that the corresponding anions can support the four requisite steps. We show here that the wild-type halogenase SyrB2 can indeed direct aliphatic nitration and azidation reactions by the same chemical logic. The discovery and enhancement by mutagenesis of these previously unknown reaction types suggests unrecognized or untapped versatility in ferryl-mediated enzymatic C–H-bond activation. PMID:24463698

  7. Exploring 3D structural influences of aliphatic and aromatic chemicals on α-cyclodextrin binding.

    PubMed

    Linden, Lukas; Goss, Kai-Uwe; Endo, Satoshi

    2016-04-15

    Binding of solutes to macromolecules is often influenced by steric effects caused by the 3D structures of both binding partners. In this study, the 1:1 α-cyclodextrin (αCD) binding constants (Ka1) for 70 organic chemicals were determined to explore the solute-structural effects on the αCD binding. Ka1 was measured using a three-part partitioning system with either a headspace or a passive sampler serving as the reference phase. The Ka1 values ranged from 1.08 to 4.97 log units. The results show that longer linear aliphatic chemicals form more stable complexes than shorter ones, and that the position of the functional group has a strong influence on Ka1, even stronger than the type of the functional group. Comparison of linear and variously branched aliphatic chemicals indicates that having a sterically unhindered alkyl chain is favorable for binding. These results suggest that only one alkyl chain can enter the binding cavity. Relatively small aromatic chemicals such as 1,3-dichlorobenzene bind to αCD well, while larger ones like tetrachlorobenzene and 3-ring aromatic chemicals show only a weak interaction with αCD, which can be explained by cavity exclusion. The findings of this study help interpret cyclodextrin binding data and facilitate the understanding of binding processes to macromolecules.

  8. New aliphatic glycerophosphoryl-containing polyurethanes: synthesis, platelet adhesion and elution cytotoxicity studies.

    PubMed

    Acetti, Daniela; D'Arrigo, Paola; Giordano, Carmen; Macchi, Piero; Servi, Stefano; Tessaro, Davide

    2009-04-01

    in this study new poly(ether)urethanes (PeUs) based on aliphatic diisocyanates were synthesized with phospholipid-like residues as chain extenders. The primary objective was to prepare new polyurethanes from diisocyanates that are less toxic than the aromatic ones widely used in medical-grade polyurethanes, in order to investigate the effect of the different aromatic or aliphatic hard segment content on the final properties of the materials. Some glycerophospho residues were simultaneously introduced to enhance the hemocompatibility of these materials. Polymers were prepared by a conventional two-step solution polymerization procedure using hexamethylene diisocyanate (HDi) and dodecametilendiisocyanate (DDi) and poly(1,4-butanediol) with molecular weight 1000 to form prepolymers, which were subsequently polymerized with 1-glycerophosphorylcholine (1-GPC) or glycerophosphorylserine (GPS) to act as chain extenders. The reference polymers bearing 1,4-butandiol (BD) were also synthesized. The polymers obtained were characterized by fourier transform infrared spectroscopy (fT-iR), nuclear magnetic resonance (1H nmR), and differential scanning calorimetry (DSC). The hemocompatibility of synthesized segmented polyurethanes was preliminarily investigated by platelet-rich plasma contact studies and related scanning electron microscopy (Sem) photographs as well as by cell viability assay after cell exposure to material elutions to assess the effect of any toxic leachables coming out from the samples. Two of the polymers gave interesting results, suggesting the desirability of further investigation into their possible use in biomedical devices. PMID:19569028

  9. Nanostructure to microstructure self-assembly of aliphatic polyurethanes: the effect on mechanical properties.

    PubMed

    Mishra, Abhinay; Aswal, Vinod K; Maiti, Pralay

    2010-04-29

    We report the step by step self-assembly from nanostructure to microstructure (bottom-up approach through X-ray diffraction (1.6 nm), small angle neutron scattering (SANS) (11.6 nm), atomic force microscopy (70 nm smaller crystallite from enlarged image and 450 nm greater crystallites), and polarizing optical microscope (2 microm)) of aliphatic polyurethanes (PU) in contrast to aromatic polyurethanes depending on hard segment content (HSC). Polyurethanes of 10 to 80% HSC have been synthesized by using appropriate amount of polyol and chain extender. The effect of self-assembled patterns on mechanical properties both in solid and liquid state has been established exhibiting structure-property relationship of supramolecular polyurethanes. The crystallinity enhances but the degradation temperature decreases with increasing HSC. The characteristic length (measure of gap between lamellar crystallites), as revealed from SANS, gradually decreases with increasing HSC suggesting compactness of the crystallites through extensive hydrogen bonding. The Young's modulus increases with increasing HSC with a percolation threshold of hard segment (50%) while the toughness improves up to 30% HSC followed by gradual decrease in presence of bigger crystallites which promote brittle fracture. The origin of self-assembly in aliphatic PUs has been demonstrated through electronic structure calculations to form a loop structure with minimum intermolecular distance (2.2 A) while that distance is quite large in aromatic polyurethanes (4.6 A) that cannot form hydrogen bonds. The unique splintering of domain structure and its subsequent reformation under dynamic shear experiment has been established. PMID:20361786

  10. Spatial variations and chronologies of aliphatic hydrocarbons in Lake Michigan sediments.

    PubMed

    Doskey, P V

    2001-01-15

    Four sediment cores were collected in fine-grained depositional areas of the southern basin of Lake Michigan. Spatial variations of aliphatic hydrocarbons in surficial sediments were consistent with a lakeward movement of riverine sediments in a series of resuspension-settling cycles in which an unresolved complex mixture (UCM) of hydrocarbons associated with dense sediments is deposited in nearshore areas, fine-grained sediments of terrestrial origin accumulate in the deep basin, and planktonic hydrocarbons are depleted by microbial degradation during transport to the deep basin. The rate of accumulation of the UCM (a marker of petroleum residues) in deep basin sediments has increased by more than an order of magnitude since 1880, from 60 microg m(-2) x a(-1) to approximately 960 microg m(-2) x a(-1) in 1980. Crude estimates of the atmospheric loading of the UCM (1100 microg m(-2) x a(-1)) indicate that accumulations in deep-basin sediments might be supported by atmospheric deposition. Agreement was poor between the atmospheric flux of the terrestrial n-alkanes (sigmaC25, C27, C29, C31) to the deep basin (3200 microg m(-2) x a(-1)) and the sediment accumulation rate (660 microg m(-2) x a(-1)). Understanding of atmospheric fluxes, estimated from the very few available data, would be improved by more frequent measurement of the levels of aliphatic hydrocarbons in air and precipitation and a better knowledge of the particle deposition velocities and precipitation scavenging coefficients.

  11. Halides with Fifteen Aliphatic C–H···Anion Interaction Sites

    NASA Astrophysics Data System (ADS)

    Shi, Genggongwo; Aliakbar Tehrani, Zahra; Kim, Dongwook; Cho, Woo Jong; Youn, Il-Seung; Lee, Han Myoung; Yousuf, Muhammad; Ahmed, Nisar; Shirinfar, Bahareh; Teator, Aaron J.; Lastovickova, Dominika N.; Rasheed, Lubna; Lah, Myoung Soo; Bielawski, Christopher W.; Kim, Kwang S.

    2016-07-01

    Since the aliphatic C–H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C–H (Cali–H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic Cali–H groups. An X-ray structure of imidazolium-based scaffolds using Cali–H···A‑ interactions (A‑ = anion) shows that a halide anion is directly interacting with fifteen Cali–H groups (involving eleven hydrogen bonds, two bidentate hydrogen-bond-type binding interactions and two weakly hydrogen-bonding-like binding interactions). Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The Cali–H···A‑ interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms.

  12. Mixed aromatic-aliphatic organic nanoparticles as carriers of unidentified infrared emission features.

    PubMed

    Kwok, Sun; Zhang, Yong

    2011-11-01

    Unidentified infrared emission bands at wavelengths of 3-20 micrometres are widely observed in a range of environments in our Galaxy and in others. Some features have been identified as the stretching and bending modes of aromatic compounds, and are commonly attributed to polycyclic aromatic hydrocarbon molecules. The central argument supporting this attribution is that single-photon excitation of the molecule can account for the unidentified infrared emission features observed in 'cirrus' clouds in the diffuse interstellar medium. Of the more than 160 molecules identified in the circumstellar and interstellar environments, however, not one is a polycyclic aromatic hydrocarbon molecule. The detections of discrete and broad aliphatic spectral features suggest that the carrier of the unidentified infrared emission features cannot be a pure aromatic compound. Here we report an analysis of archival spectroscopic observations and demonstrate that the data are most consistent with the carriers being amorphous organic solids with a mixed aromatic-aliphatic structure. This structure is similar to that of the organic materials found in meteorites, as would be expected if the Solar System had inherited these organic materials from interstellar sources.

  13. Aliphatic and aromatic hydrocarbons in different sized aerosols over the Mediterranean Sea: Occurrence and origin

    NASA Astrophysics Data System (ADS)

    Sicre, M. A.; Marty, J. C.; Saliot, A.; Aparicio, X.; Grimalt, J.; Albaiges, J.

    Marine aerosols were collected using a five-stage cascade impactor during the PHYCEMED II cruise in the Western Mediterranean Sea (October 1983). Their composition in aliphatic and aromatic hydrocarbons (HCs) was analyzed, representing the first time that concentrations of polynuclear aromatic HCs (PAH) are reported in relation to particle size for aerosols of remote marine areas. The HC concentrations were found to be dependent on the origin of the air masses. They were higher for air coming from North European countries than for air originating in the Atlantic and the South of Spain. The concentrations range between 7 and 14 ng m -3for n-alkanes and between 0.2 and 0.4 ng m -3for total PAH. Based on molecular criteria, several sources for these HCs have been identified: continental higher plant waxes, petroleum and pyrolysis (namely coal combustion and vehicular exhausts). Mass medium equivalent diameters (MMED) for the naturally derived n-alkanes are in the 1.79-2.53 μm range, indicating an origin related with the emission of large particles from higher plant waxes or from soil dusts. In contrast, MMED for the anthropogenic HCs, both aliphatic and aromatic, are smaller than the micron, suggesting initial emission of PAH through pyrolytic processes in the vapor phase followed by condensation onto larger sub-μm particles.

  14. Halides with Fifteen Aliphatic C-H···Anion Interaction Sites.

    PubMed

    Shi, Genggongwo; Aliakbar Tehrani, Zahra; Kim, Dongwook; Cho, Woo Jong; Youn, Il-Seung; Lee, Han Myoung; Yousuf, Muhammad; Ahmed, Nisar; Shirinfar, Bahareh; Teator, Aaron J; Lastovickova, Dominika N; Rasheed, Lubna; Lah, Myoung Soo; Bielawski, Christopher W; Kim, Kwang S

    2016-01-01

    Since the aliphatic C-H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C-H (Cali-H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic Cali-H groups. An X-ray structure of imidazolium-based scaffolds using Cali-H···A(-) interactions (A(-) = anion) shows that a halide anion is directly interacting with fifteen Cali-H groups (involving eleven hydrogen bonds, two bidentate hydrogen-bond-type binding interactions and two weakly hydrogen-bonding-like binding interactions). Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The Cali-H···A(-) interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms. PMID:27444513

  15. Determination of aliphatic low-molecular-weight and biogenic amines by capillary zone electrophoresis.

    PubMed

    Fekete, Agnes; Lahaniatis, Majlinda; Lintelmann, Jutta; Schmitt-Kopplin, Philippe

    2008-01-01

    Low-molecular-weight (LMW) aliphatic amines play a key role in the global nitrogen cycle, are involved in nutrient transfer, and act as buffer in the ecosystem. They are widely used as intermediates in chemical synthesis and were shown to cause occupational asthma. Biogenic amines occur in all living organisms and have an effect on the cell growth, although at high concentrations they can be toxic; some are used as cancer markers in health protection or as spoilage markers in foods. Their identification and quantification from different matrices such as human tissues or foods is of high importance. The electrophoretic separation of amines is possible as cations as a result of their high basicity; their detection, however, is more difficult because these amines contain no chromophore group. Indirect ultraviolet (UV) detection is the first presented possibility and widely used for the separation of nonderivatized amines. Otherwise, derivatization of the amines is necessary to directly detect them with laser-induced fluorescence (LIF) detection. Other detection modes such as pulse amperometric, chemiluminescence, or mass spectrometry have been also used for the determination of LMW and biogenic amines, but not on a routine basis. In this chapter, three capillary electrophoretic methods with indirect UV and LIF detection for determination of LMW aliphatic and biogenic amines are described.

  16. Decomposition mechanisms of trinitroalkyl compounds: a theoretical study from aliphatic to aromatic nitro compounds.

    PubMed

    Fayet, Guillaume; Rotureau, Patricia; Minisini, Benoit

    2014-04-14

    The chemical mechanisms involved in the decomposition of trinitroethyl compounds were studied for both aliphatic and aromatic derivatives using density functional theory calculations. At first, in the case of 1,1,1-trinitrobutane, used as a reference molecule, two primary channels were highlighted among the five investigated ones: the breaking of the C-N bond and the HONO elimination. Then, the influence of various structural parameters was studied for these two reactions by changing the length of the carbon chain, adding substituents or double bonds along the carbon chain. If some slight changes in activation energies were observed for most of these features, no modification of the competition between the two investigated reactions was highlighted and the breaking of the C-N bond remained the favoured mechanism. At last, the reactions involving the trinitroalkyl fragments were highlighted to be more competitive than reactions involving nitro groups linked to aromatic cycles in two aromatic systems (4-(1,1,1-trinitrobutyl)-nitrobenzene and 2-(1,1,1-trinitrobutyl)-nitrobenzene). This showed that aromatic nitro compounds with trinitroalkyl derivatives decompose from their alkyl part and may be considered more likely as aliphatic than as aromatic regarding the initiation of their decomposition process.

  17. Halides with Fifteen Aliphatic C–H···Anion Interaction Sites

    PubMed Central

    Shi, Genggongwo; Aliakbar Tehrani, Zahra; Kim, Dongwook; Cho, Woo Jong; Youn, Il-Seung; Lee, Han Myoung; Yousuf, Muhammad; Ahmed, Nisar; Shirinfar, Bahareh; Teator, Aaron J.; Lastovickova, Dominika N.; Rasheed, Lubna; Lah, Myoung Soo; Bielawski, Christopher W.; Kim, Kwang S.

    2016-01-01

    Since the aliphatic C–H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C–H (Cali–H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic Cali–H groups. An X-ray structure of imidazolium-based scaffolds using Cali–H···A− interactions (A− = anion) shows that a halide anion is directly interacting with fifteen Cali–H groups (involving eleven hydrogen bonds, two bidentate hydrogen-bond-type binding interactions and two weakly hydrogen-bonding-like binding interactions). Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The Cali–H···A− interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms. PMID:27444513

  18. Permittivity of naphthenic acid-water mixture.

    PubMed

    Mishra, Sabyasachi; Meda, Venkatesh; Dalai, Ajay

    2007-01-01

    Naphthenic acid (NA) is predominantly a mono-carboxylic acid obtained as a by-product of petroleum refining with variable composition and ingredients. It is reported that water affected by processes in the petroleum industries generally contains 40-120 mg IL of naphthenic acid which is considered to be in the range of toxicity to human consumption [Clemente et. al, 2005; McMartin, 2003]. This contaminated water needs treatment before its use as drinking water by remote communities. Recent literature suggests that NAs could be separated from diesel fuel using microwave radiation [Lingzhao et. al, 2004]. Removal of naphthenic acid from vacuum cut #1 distillate oil of Daqing using microwaves has also been reported by Huang et. al [2006]. The microwave treatment can be applied to drinking water containing small concentrations of naphthenic acid. In this case permittivity information is useful in designing a microwave applicator and modeling studies. Permittivity measurements were done using a HP 8510 Vector Network Analyzer and coaxial probe reflection method to study the dielectric properties of naphthenic acid in water. The effects of process variables such as frequency, concentration and temperature on dielectric properties were determined. PMID:18161419

  19. Permittivity of naphthenic acid-water mixture.

    PubMed

    Mishra, Sabyasachi; Meda, Venkatesh; Dalai, Ajay

    2007-01-01

    Naphthenic acid (NA) is predominantly a mono-carboxylic acid obtained as a by-product of petroleum refining with variable composition and ingredients. It is reported that water affected by processes in the petroleum industries generally contains 40-120 mg IL of naphthenic acid which is considered to be in the range of toxicity to human consumption [Clemente et. al, 2005; McMartin, 2003]. This contaminated water needs treatment before its use as drinking water by remote communities. Recent literature suggests that NAs could be separated from diesel fuel using microwave radiation [Lingzhao et. al, 2004]. Removal of naphthenic acid from vacuum cut #1 distillate oil of Daqing using microwaves has also been reported by Huang et. al [2006]. The microwave treatment can be applied to drinking water containing small concentrations of naphthenic acid. In this case permittivity information is useful in designing a microwave applicator and modeling studies. Permittivity measurements were done using a HP 8510 Vector Network Analyzer and coaxial probe reflection method to study the dielectric properties of naphthenic acid in water. The effects of process variables such as frequency, concentration and temperature on dielectric properties were determined.

  20. Kinetics of formation and dissociation of aquocobalt(III) complexes with some carboxylic acids in acid perchlorate solution.

    PubMed

    Davies, Geoffrey

    2007-06-21

    The rates of formation and dissociation of monocarboxylic complexes of aquocobalt(III) cations with propionic, malonic, and 2-ethylmalonic acids have been measured with the stopped-flow method over a range of concentrations and temperatures in acid perchlorate media at an ionic strength 3.0 M. Although the rate constants for reactions of CoOHaq2+ with neutral ligands cover only a small range, indicating a dissociative mechanism, the associated activation parameters change cooperatively. These variations are discussed in terms of differences in the structure, proton distribution, and rates of water loss in the ion-pair precursors for the different ligands. Similar activation enthalpies of dissociation indicate a common mode of coordination, and the positive activation entropies for dissociation are consistent with a neutral leaving group.

  1. Extraction chemistry of fermentation product carboxylic acid

    SciTech Connect

    Kertes, A.S.; King, C.J.

    1986-02-01

    Within the framework of a program aiming to improve the existing extractive recovery technology of fermentation products, the state of the art is critically reviewed. The acids under consideration are propionic, lactic, pyruvic, succinic, fumaric, maleic, malic, itaconic, tartaric, citric, and isocitric, all obtained by the aerobic fermentation of glucose via the glycolytic pathway and glyoxylate bypass. With no exception, it is the undissociated monomeric acid that is extracted into carbon-bonded and phosphorus-bonded oxygen donor extractants. In the organic phase, the acids are usually dimerized. The extractive transfer process obeys the Nernst law, and the measured partition coefficients range from about 0.003 for aliphatic hydrocarbons to about 2 to 3 for aliphatic alcohols and ketones to about 10 or more for organophosphates. Equally high distribution ratios are measured when long-chain tertiary amines are employed as extractants, forming bulky salts preferentially soluble in the organic phase. 123 references.

  2. A fatty acyl-CoA reductase highly expressed in the head of honey bee (Apis mellifera) involves biosynthesis of a wide range of aliphatic fatty alcohols.

    PubMed

    Teerawanichpan, Prapapan; Robertson, Albert J; Qiu, Xiao

    2010-09-01

    Honey bees (Apis mellifera) are social insects which have remarkable complexity in communication pheromones. These chemical signals comprise a mixture of hydrocarbons, wax esters, fatty acids, aldehydes and alcohols. In this study, we detected several long chain aliphatic alcohols ranging from C18-C32 in honey bees and the level of these alcohols varied in each body segment. C18:0Alc and C20:0Alc are more pronounced in the head, whereas C22:0Alc to C32Alc are abundant in the abdomen. One of the cDNAs coding for a fatty acyl-CoA reductase (AmFAR1) involved in the synthesis of fatty alcohols was isolated and characterized. AmFAR1 was ubiquitously expressed in all body segments with the predominance in the head of honey bees. Heterologous expression of AmFAR1 in yeast revealed that AmFAR1 could convert a wide range of fatty acids (14:0-22:0) to their corresponding alcohols, with stearic acid 18:0 as the most preferred substrate. The substrate preference and the expression pattern of AmFAR1 were correlated with the level of total fatty alcohols in bees. Reconstitution of the wax biosynthetic pathway by heterologous expression of AmFAR1, together with Euglena wax synthase led to the high level production of medium to long chain wax monoesters in yeast.

  3. Direct β-C(sp(3))-H Functionalization of Aliphatic Amines to α,β-Unsaturated Imines, Aldehydes, and Chromenes.

    PubMed

    Mandal, Sumana; Mahato, Sujit; Jana, Chandan K

    2015-08-01

    A metal-free method for direct β-C(sp(3))-H functionalization of aliphatic amine was developed. The method is based on a reaction that yields enamine directly from the corresponding aliphatic amine, which otherwise requires the aid of metallic reagent and/or external oxidant. The reaction is operationally simple, general, and highly efficient in functionalizing both cyclic and acyclic amines. Structurally diverse unsaturated imines were obtained from N-heterocycles, while acyclic amines provided 2-alkyl cinnamaldehyde and benzopyran derivatives with excellent E/Z-selectivity. PMID:26204435

  4. Polycyclic aromatic and aliphatic hydrocarbons pollution at the coast of Aliağa (Turkey) ship recycling zone.

    PubMed

    Neşer, Gökdeniz; Kontas, Aynur; Unsalan, Deniz; Altay, Oya; Darılmaz, Enis; Uluturhan, Esin; Küçüksezgin, Filiz; Tekoğul, Nermin; Yercan, Funda

    2012-05-01

    Aliağa Bay is one of the most important maritime zones of Turkey where shipping activity, shipbreaking industry, steel works and petrochemical complexes exist together. Polycyclic aromatic hydrocarbons (PAHs) and aliphatic hydrocarbons in sediment of the Aliağa Bay were investigated to evaluate an environmental risk assessment from PAHs contamination in 2009-2010. Aliphatic and PAHs diagnostic ratios were showed to be mainly petroleum-originated and pyrolitic contaminations, respectively. The TEL/PEL analysis suggests that Aliağa sediments were likely to be contaminated by acutely toxic PAH compounds.

  5. A Bioinspired Catalytic Aerobic Oxidative C–H Functionalization of Primary Aliphatic Amines: Synthesis of 1,2-Disubstituted Benzimidazoles

    PubMed Central

    Nguyen, Khac Minh Huy; Largeron, Martine

    2015-01-01

    Aerobic oxidative C–H functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. PMID:26206475

  6. Complete genome of Zhongshania aliphaticivorans SM-2(T), an aliphatic hydrocarbon-degrading bacterium isolated from tidal flat sediment.

    PubMed

    Jia, Baolei; Jeong, Hye Im; Kim, Kyung Hyun; Jeon, Che Ok

    2016-05-20

    Zhongshania aliphaticivorans SM-2(T), a degrader of aliphatic hydrocarbons, is a Gram-negative, rod-shaped, flagellated, facultatively aerobic bacterium. Here, we report the genome sequence of strain SM-2(T), which has a size of 4,204,359bp with 44 tRNAs, 9 rRNAs, and 3664 protein-coding genes. In addition, several genes encoding aliphatic hydrocarbon degraders (alkane 1-monooxygenase, haloalkane dehalogenase, and cytochrome P450) were detected in the genome shedding light on the function of pollutants degradation.

  7. Bio-olefins from unsaturated fatty acids via tandem catalysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A new catalytic route to bio-olefins from unsaturated fatty acids will be described. At the heart of the process, the catalyst apparently functions in a tandem mode by both dynamically isomerizing the positions of double bonds in an aliphatic chain and, subsequently, decarboxylating specific isomers...

  8. Aromatic and aliphatic CH hydrogen bonds fight for chloride while competing alongside ion pairing within triazolophanes.

    PubMed

    Hua, Yuran; Ramabhadran, Raghunath O; Uduehi, Esther O; Karty, Jonathan A; Raghavachari, Krishnan; Flood, Amar H

    2011-01-01

    Triazolophanes are used as the venue to compete an aliphatic propylene CH hydrogen-bond donor against an aromatic phenylene one. Longer aliphatic C-H...Cl(-) hydrogen bonds were calculated from the location of the chloride within the propylene-based triazolophane. The gas-phase energetics of chloride binding (ΔG(bind) , ΔH(bind) , ΔS(bind) ) and the configurational entropy (ΔS(config) ) were computed by taking all low-energy conformations into account. Comparison between the phenylene- and propylene-based triazolophanes shows the computed gas-phase free energy of binding decreased from ΔG(bind) =-194 to -182 kJ mol(-1) , respectively, with a modest enthalpy-entropy compensation. These differences were investigated experimentally. An (1) H NMR spectroscopy study on the structure of the propylene triazolophane's 1:1 chloride complex is consistent with a weaker propylene CH hydrogen bond. To quantify the affinity differences between the two triazolophanes in dichloromethane, it was critical to obtain an accurate binding model. Four equilibria were identified. In addition to 1:1 complexation and 2:1 sandwich formation, ion pairing of the tetrabutylammonium chloride salt (TBA(+) ⋅Cl(-) ) and cation pairing of TBA(+) with the 1:1 triazolophane-chloride complex were observed and quantified. Each complex was independently verified by ESI-MS or diffusion NMR spectroscopy. With ion pairing deconvoluted from the chloride-receptor binding, equilibrium constants were determined by using (1) H NMR (500 μM) and UV/Vis (50 μM) spectroscopy titrations. The stabilities of the 1:1 complexes for the phenylene and propylene triazolophanes did not differ within experimental error, ΔG=(-38±2) and (-39±1) kJ mol(-1) , respectively, as verified by an NMR spectroscopy competition experiment. Thus, the aliphatic CH donor only revealed its weaker character when competing with aromatic CH donors within the propylene-based triazolophane.

  9. Aliphatic and polycyclic aromatic hydrocarbons characterisation of Coimbra and Oporto PM2.5 urban aerosol

    NASA Astrophysics Data System (ADS)

    Rocha, A. C.; Mirante, F.; Gonçalves, C.; Nunes, T.; Alves, C.; Evtyugina, M.; Kowacz, M.; Pio, C.; Rocha, C.; Vasconcelos, T.

    2009-04-01

    The concentration of organic pollutants in urban areas is mostly due to incomplete combustion from vehicles, industries and domestic heating. Some of these compounds, principally the aliphatic (ALIPH) and polycyclic aromatic hydrocarbons (PAHs) promote harmful effects in human health. The determination of the ALIPH and PAHs concentration levels and their possible emission sources are useful for air quality management and source apportionment studies. In order to estimate and compare the ambient concentrations and establish the main sources of these compounds, the fine fraction of the atmospheric particulate matter (PM2.5) was collected simultaneously in Oporto and Coimbra during summer and winter seasons using a high volume sampler. The organic compounds were extracted from the particulate matter, under reflux with dichloromethane and the total organic extract (TOE) was fractionated by flash chromatography using five different eluents with increasing polarity. The hydrocarbon fractions were analysed by gas chromatography/mass spectrometry (GC/MS). Here we present and discuss the qualitative and quantitative composition of the aliphatic and aromatic fractions present in PM2.5 samples from both cities. The homologous series of C14 to C34 n-alkanes, isoprenoid hydrocarbons (pristane and phytane), PAHs and some petroleum markers have been identified and quantified. With the purpose of identifying the possible sources, various molecular diagnostic ratios were calculated. The global carbon preference index (CPI) closer to the unity, the large concentration of the unresolved complex mixture (UCM) and the presence of PAHs indicate that motor vehicle exhaust was the main emission source of the aliphatic and polycyclic aromatic fractions of Oporto and Coimbra aerosol, especially in the first city. Also, the remarkable presence of petroleum biomarkers such, as hopanes, confirms the previous results. Concentration ratios between PAHs were calculated and used to assign emission

  10. Validation of a solvent-free sampler for the determination of low molecular weight aliphatic isocyanates under thermal degradation conditions.

    PubMed

    Boutin, M; Lesage, J; Ostiguy, C; Pauluhn, J

    2005-09-01

    During the thermal degradation of 1,6-hexamethylenediiso- cyanate-based (HDI) car paint, the eight most abundant isocyanates generated are isocyanic acid, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, and 1,6-hexamethylenediisocyanate. For the first time, a method using solvent-free samplers is proposed and validated for the simultaneous sampling of all these isocyanates. The sampling efficiency during thermal degradation of car paint can be affected by the formation of dust and aerosols and by the emission of many chemicals, such as isocyanic acid, anhydrides, amines, and alcohols that consume the reagent or interfere in the derivatization procedure. Sampling was performed using cassettes containing two 1-(2-methoxyphenyl)piperazine (MOPIP)-coated glass fiber filters (MFs) (approximately 4.9 mg per filter) and compared with bubblers containing 15 mL of MOPIP solution in toluene (1.0 mg/mL(-1)) and with bubblers backed with MFs. A DIN 53436 laboratory scale furnace was used to generate the isocyanates under thermal degradation conditions. For an aliphatic isocyanate concentration of approximately 42 microg(NCO) m(-3), no significant difference in sampling efficiency was observed between the three techniques studied, thus confirming the sampling efficiency of the MFs. The samples were analyzed using high-performance liquid chromatography coupled with electrospray/tandem mass spectrometry. Quantification was performed in daughter mode monitoring (MOPIP+H)(+) fragments. For concentrations between 0.013 microg(NCO) mL(-1) and 0.52 microg(NCO) mL(-1) for the monoisocyanates, and between 0.026 microg(NCO) mL(-1) and 1.04 microg(NCO) mL(-1) for the HDI, the correlation coefficients were in the 0.9974-0.9996 range (n = 18). Analytical reproducibility and precision were better than 95.4% and 94.9%, respectively, for all the isocyanates. The instrumental detection limits, defined as three times the standard

  11. Validation of a solvent-free sampler for the determination of low molecular weight aliphatic isocyanates under thermal degradation conditions.

    PubMed

    Boutin, M; Lesage, J; Ostiguy, C; Pauluhn, J

    2005-09-01

    During the thermal degradation of 1,6-hexamethylenediiso- cyanate-based (HDI) car paint, the eight most abundant isocyanates generated are isocyanic acid, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, pentyl isocyanate, hexyl isocyanate, and 1,6-hexamethylenediisocyanate. For the first time, a method using solvent-free samplers is proposed and validated for the simultaneous sampling of all these isocyanates. The sampling efficiency during thermal degradation of car paint can be affected by the formation of dust and aerosols and by the emission of many chemicals, such as isocyanic acid, anhydrides, amines, and alcohols that consume the reagent or interfere in the derivatization procedure. Sampling was performed using cassettes containing two 1-(2-methoxyphenyl)piperazine (MOPIP)-coated glass fiber filters (MFs) (approximately 4.9 mg per filter) and compared with bubblers containing 15 mL of MOPIP solution in toluene (1.0 mg/mL(-1)) and with bubblers backed with MFs. A DIN 53436 laboratory scale furnace was used to generate the isocyanates under thermal degradation conditions. For an aliphatic isocyanate concentration of approximately 42 microg(NCO) m(-3), no significant difference in sampling efficiency was observed between the three techniques studied, thus confirming the sampling efficiency of the MFs. The samples were analyzed using high-performance liquid chromatography coupled with electrospray/tandem mass spectrometry. Quantification was performed in daughter mode monitoring (MOPIP+H)(+) fragments. For concentrations between 0.013 microg(NCO) mL(-1) and 0.52 microg(NCO) mL(-1) for the monoisocyanates, and between 0.026 microg(NCO) mL(-1) and 1.04 microg(NCO) mL(-1) for the HDI, the correlation coefficients were in the 0.9974-0.9996 range (n = 18). Analytical reproducibility and precision were better than 95.4% and 94.9%, respectively, for all the isocyanates. The instrumental detection limits, defined as three times the standard

  12. The Lewis-acid-catalyzed synthesis of hyperbranched poly(glycerol-diacid)s in toluene

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The first examples of monomeric glycerol-derived hyperbranched polyesters produced in a non-polar solvent system are reported here. The polymers were made by the Lewis acid (dibutyltin(IV)oxide)-catalyzed polycondensation of glycerol with either succinic acid (n (aliphatic chain length)=2), glutari...

  13. Gas phase C{sub 2}-C{sub 10} organic acids concentrations in the Los Angeles atmosphere

    SciTech Connect

    Nolte, C.G.; Fraser, M.P.; Cass, G.R.

    1999-02-15

    The atmospheric concentrations of gas-phase C{sub 2}--C{sub 10} monocarboxylic and benzoic acids are reported in samples collected during a severe Los Angeles area photochemical smog episode. Average urban concentrations are 10--50 {times} greater than concentrations observed at a remote background location, indicating an anthropogenic origin for these compounds. Average urban concentrations during the episode were 16.1 {micro}g m{sup {minus}3} (6.6 ppb) for acetic acid and 1.67 {micro}g m{sup {minus}3} (0.55 ppb) for propionic acid, with progressively lesser amounts as the carbon chain length of the acids is increased. Spatial and diurnal variations in atmospheric organic acids concentrations point to the importance of both direct emissions from primary sources and formation by photochemical reaction of precursor compounds.

  14. Complexes of ruthenium and rhodium with aliphatic amines in the catalysis of hydrogenation of unsaturated hydrocarbons

    SciTech Connect

    Turisbekova, K.K.; Shuikina, L.P.; Parenago, O.P.; Frolov, V.F.

    1989-02-01

    The authors synthesized new catalysts highly active in the hydrogenations of unsaturated hydrocarbons, based on complexes of ruthenium and rhodium with higher aliphatic amines, which are soluble in aromatic solvents. The complexes acquired catalytic activity in hydrogenation as a result of their treatment with diisobutyl aluminum hydride. Olefins (1-hexene, cyclopentene, cyclohexene) or dienes (isoprene) were used as the unsaturated compounds. For the ruthenium based catalysts, the highest activity was observed during the hydrogenation of 1-hexene. For the rhodium-based catalysts, the activity in the hydrogenation of olefins and dienes was approximately the same. In the case of the rhodium complex catalysts, the hydrogenation of 1-hexene was accompanied by a side-reaction consisting in isomerization into olefins with inner double bonds.

  15. Low-temperature microchip nonaqueous capillary electrophoresis of aliphatic primary amines: applications to Titan chemistry.

    PubMed

    Cable, Morgan L; Stockton, Amanda M; Mora, Maria F; Willis, Peter A

    2013-01-15

    We demonstrate microchip nonaqueous capillary electrophoresis (μNACE) analysis of primary aliphatic amines (C1-C18) in ethanol down to -20 °C as a first step in adapting microfluidic protocols for in situ analysis on Titan. To our knowledge, this is the first report of a nonaqueous separation at -20 °C on-chip. Limits of detection (LODs) ranged from 1.0 nM to 2.6 nM, and we identified several primary amines ranging in length from C2 to C16 in Titan aerosol analogue (tholin) samples; new amines were also detected in a tholin sample exposed to oxygen and liquid water. This preliminary work validates the sensitivity and efficacy of microfluidic chemical analysis of complex organics with relevance to Titan aerosols and surface deposits. PMID:23214444

  16. Atmospheric chemistry of toxic contaminants 4. Saturated halogenated aliphatics: Methyl bromide, epichlorhydrin, phosgene

    SciTech Connect

    Grosjean, D. )

    1991-01-01

    Mechanisms are outlined for the reactions that contribute to in-situ formation and atmospheric removal of the saturated halogenated aliphatic contaminants methyl bromide, epichlorhydrin, and phosgene. In-situ formation is important only for phosgene and involves the reaction of OH with chloroethenes and other chlorinated hydrocarbons. A ranking of these phosgene precursors is given using data for precursor ambient concentrations and chemical reactivity. The three toxic compounds studied are long-lived in the atmosphere, where removal of phosgene and methyl bromide by chemical reactions is negligibly slow. Epichlorhydrin is removed slowly by reaction with OH, leading to formaldehyde, chloroacetaldehyde, and the chlorinated peroxyacyl nitrate CH{sub 2}ClC(O)OONO{sub 2}.

  17. Branched aliphatic alkanes with quaternary substituted carbon atoms in modern and ancient geologic samples

    PubMed Central

    Kenig, Fabien; Simons, Dirk-Jan H.; Crich, David; Cowen, James P.; Ventura, Gregory T.; Rehbein-Khalily, Tatiana; Brown, Todd C.; Anderson, Ken B.

    2003-01-01

    A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-dimethylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65°C) deep-sea hydrothermal waters and Late Cretaceous black shales. 5,5-Diethylalkanes were also observed in modern and Holocene marine shelf sediments and in shales spanning the last 800 million years of the geological record. The carbon number distribution of BAQCs indicates a biological origin. These compounds were observed but not identified in previous studies of 2.0 billion- to 2.2 billion-year-old metasediments and were commonly misidentified in other sediment samples, indicating that BAQCs are widespread in the geological record. The source organisms of BAQCs are unknown, but their paleobiogeographic distribution suggests that they have an affinity for sulfides and might be nonphotosynthetic sulfide oxidizers. PMID:14551322

  18. Branched aliphatic alkanes with quaternary substituted carbon atoms in modern and ancient geologic samples.

    PubMed

    Kenig, Fabien; Simons, Dirk-Jan H; Crich, David; Cowen, James P; Ventura, Gregory T; Rehbein-Khalily, Tatiana; Brown, Todd C; Anderson, Ken B

    2003-10-28

    A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-dimethylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65 degrees C) deep-sea hydrothermal waters and Late Cretaceous black shales. 5,5-Diethylalkanes were also observed in modern and Holocene marine shelf sediments and in shales spanning the last 800 million years of the geological record. The carbon number distribution of BAQCs indicates a biological origin. These compounds were observed but not identified in previous studies of 2.0 billion- to 2.2 billion-year-old metasediments and were commonly misidentified in other sediment samples, indicating that BAQCs are widespread in the geological record. The source organisms of BAQCs are unknown, but their paleobiogeographic distribution suggests that they have an affinity for sulfides and might be nonphotosynthetic sulfide oxidizers. PMID:14551322

  19. Branched aliphatic alkanes with quaternary substituted carbon atoms in modern and ancient geologic samples.

    SciTech Connect

    Kenig, F.; Simons, D.-J. H.; Crich, D.; Cowen, J. P.; Ventura, G. T.; Rehbein-Khalily, T.; Brown, T. C.; Anderson, K. B.; Chemistry; Univ. of Illinois at Chicago; Univ. of Hawaii

    2003-01-01

    A pseudohomologous series of branched aliphatic alkanes with a quaternary substituted carbon atom (BAQCs, specifically 2,2-di-methylalkanes and 3,3- and 5,5-diethylalkanes) were identified in warm (65{sup o}C) deep-sea hydrothermal waters and Late Cretaceous black shales. 5,5-Diethylalkanes were also observed in modern and Holocene marine shelf sediments and in shales spanning the last 800 million years of the geological record. The carbon number distribution of BAQCs indicates a biological origin. These compounds were observed but not identified in previous studies of 2.0 billion- to 2.2 billion-year-old metasediments and were commonly misidentified in other sediment samples, indicating that BAQCs are widespread in the geological record. The source organisms of BAQCs are unknown, but their paleobiogeographic distribution suggests that they have an affinity for sulfides and might be nonphotosynthetic sulfide oxidizers.

  20. Investigation of Aromatic/Aliphatic Polyimides as Dispersants for Single Wall Carbon Nanotubes

    NASA Technical Reports Server (NTRS)

    Delozier, Donavon M.; Watson, Kent A.; Smith, Joseph G., Jr.; Clancy, Thomas C.; Connell, John W.

    2006-01-01

    Novel aromatic/aliphatic polyimides were prepared from 2,7-diamino-9,9'- dioctylfluorene (AFDA) and aromatic dianhydrides. Upon investigating the effectiveness of these polyimides for dispersing single wall carbon nanotubes (SWNTs) in solution, three were discovered to disperse SWNTs in N,N-dimethylacetamide (DMAc). Two of these polyimides, one from 3,3',4,4'-oxydiphthalic anhydride (ODPA) and one from symmetric 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), were used to prepare nanocomposites. Homogeneous polyimide/SWNT suspensions from both polymers were used in the preparation of films and fibers containing up to 1 wt% SWNTs. The samples were thermally treated to remove residual solvent and the films were characterized for SWNT dispersion by optical and high resolution scanning electron microscopy (HRSEM). Electrical and mechanical properties of the films were also determined. Electrospun fibers were examined by HRSEM to characterize SWNT alignment and orientation.

  1. Complexes pairing aliphatic amines with hydroxyl and hydroperoxyl radicals: A computational study

    NASA Astrophysics Data System (ADS)

    Solimannejad, Mohammad; Nielsen, Claus J.; Scheiner, Steve

    2008-12-01

    Quantum calculations are used to analyze the nature and strength of binding of complexes pairing aliphatic amines with the HO and HOO radicals, with particular emphasis on the comparison of HO with HOO. Complexes are stabilized by N⋯HO(O) H-bonds involving the N lone pair. The OOH radical binds more strongly in all cases than does OH, and shows a longer stretch of its OH bond, as well as a greater red shift of this bond's stretching frequency. MP2/6-311++G(3df, 3pd) binding energies vary from 28 kJ/mol for CH 3NH 2⋯HO to a maximum of 56 kJ/mol for (CH 3) 2NH⋯HOO. The reliability of a new hybrid meta exchange-correlation functional, M05-2X, compares favorably with MP2, generally better than B3LYP.

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

    SciTech Connect

    Grosjean, D. )

    1990-12-01

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

  3. Propargyl-functional aliphatic polycarbonate obtained from carbon dioxide and glycidyl propargyl ether.

    PubMed

    Hilf, Jeannette; Frey, Holger

    2013-09-01

    The synthesis of propargyl-functional poly(carbonate)s with different content of glycidyl propargyl ether (GPE) units is achieved via the copolymerization of propargyl glycidyl ether and carbon dioxide. A new type of functional poly(carbonate) synthesized directly from CO(2) and the glycidyl ether is obtained. The resulting polymers show moderate polydispersities in the range of 1.6-2.5 and molecular weights in the range of 7000-10 500 g mol(-1). The synthesized copolymers with varying number of alkyne functionalities and benzyl azide are used for the copper-catalyzed Huisgen-1,3-dipolar addition. Moreover, the presence of vicinal alkyne groups opens a general pathway to produce functional aliphatic poly(carbonate)s from a single polymer scaffold.

  4. Low-temperature microchip nonaqueous capillary electrophoresis of aliphatic primary amines: applications to Titan chemistry.

    PubMed

    Cable, Morgan L; Stockton, Amanda M; Mora, Maria F; Willis, Peter A

    2013-01-15

    We demonstrate microchip nonaqueous capillary electrophoresis (μNACE) analysis of primary aliphatic amines (C1-C18) in ethanol down to -20 °C as a first step in adapting microfluidic protocols for in situ analysis on Titan. To our knowledge, this is the first report of a nonaqueous separation at -20 °C on-chip. Limits of detection (LODs) ranged from 1.0 nM to 2.6 nM, and we identified several primary amines ranging in length from C2 to C16 in Titan aerosol analogue (tholin) samples; new amines were also detected in a tholin sample exposed to oxygen and liquid water. This preliminary work validates the sensitivity and efficacy of microfluidic chemical analysis of complex organics with relevance to Titan aerosols and surface deposits.

  5. Catalytic activity of carbon nanotubes in the conversion of aliphatic alcohols

    NASA Astrophysics Data System (ADS)

    Zhitnev, Yu. N.; Tveritinova, E. A.; Chernyak, S. A.; Savilov, S. V.; Lunin, V. V.

    2016-06-01

    Carbon nanotubes (CNTs) obtained via the catalytic pyrolysis of hexane at 750°C were studied as the catalysts in conversion of C2-C4 alcohols. The efficiency of CNTs as catalysts in dehydration and dehydrogenation of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tert-butanol was studied by means of pulse microcatalysis. The surface and structural characteristics of CNTs are investigated via SEM, TEM, DTA, BET, and XPS. CNTs are shown to be effective catalysts in the conversion of alcohols and do not require additional oxidative treatment. The regularities of the conversion of aliphatic alcohols, related to the properties of the CNTs surface and the structure of the alcohols are identified.

  6. Investigation of thermodynamic properties of hyperbranched aliphatic polyesters by inverse gas chromatography.

    PubMed

    Dritsas, G S; Karatasos, K; Panayiotou, C

    2009-12-18

    Thermodynamic properties of a series of commercial hyperbranched aliphatic polyesters (Boltorn H20, H30 and H40) were examined for the first time by inverse gas chromatography (IGC) using 13 different solvents at infinite dilution as probes. Retention data of probes were utilized for an extensive characterization of polymers, which includes the determination of the Flory-Huggins interaction parameter, the weight fraction activity coefficient as well as the total and partial solubility parameters. Analysis of the results indicated that the total and partial solubility parameters decrease with increase of temperature. Furthermore, upon increase of the molecular weight, while the hydrogen bonding component decreases, no influence on the total solubility parameter is noticed within the experimental error margins. Results from the present study while providing new insight to the thermodynamic characteristics of the examined systems, they are also expected to reflect more general aspects of the behavior of hyperbranched polymers bearing similar end-groups.

  7. Aliphatic hydrocarbons in sediment cores from the southern basin of Lake Michigan

    SciTech Connect

    Doskey, P.V.; Andren, A.W.

    1991-10-01

    Aliphatic hydrocarbons in sediments of the southern basin of Lake Michigan have planktonic, terrigenous, and petroleum residue origins. Surficial sediments collected near the eastern shore in 60-80 m of water contained more petroleum residue and planktonic hydrocarbons and exhibited less terrigenous character than sediments collected from the deepest location in the basin. Petroleum residue inputs have increased since 1900 as evidenced by a change in the flux of an unresolved complex mixture (UCM) of hydrocarbons from 6 ng/cm{sup 2}{center_dot}yr to a flux of approximately 100 ng/cm{sup 2}{center_dot}yr in 1980. Sediment profiles of the UCM exhibited subsurface concentration maxima that may be due to reduced inputs of combustion products or feeding by oligochaetes. Profiles of n-C{sub l7} and pristane indicated that planktonic n-alkanes undergo degradation in the aerobic, mixed zone of the sediments.

  8. Electrochemical oxidation of aliphatic amines and their attachment to carbon and metal surfaces.

    PubMed

    Adenier, Alain; Chehimi, Mohamed M; Gallardo, Iluminada; Pinson, Jean; Vilà, Neus

    2004-09-14

    The electrochemical oxidation of aliphatic amines (primary, secondary, and tertiary) has been investigated by cyclic voltammetry and preparative electrolysis. The oxidation mechanisms have been established, and the lifetimes of the radical cations have been measured for secondary and tertiary amines. These results have been put in parallel with the attachment of amines to glassy carbon, Au, and Pt electrodes by cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and infrared reflection-absorption spectroscopy (IRRAS). It is then possible to show that it is not the radical cation but the radical obtained after the deprotonation which reacts with the electrode surface. XPS results also point to the existence of a covalent bond between Au or Pt and the organic moiety.

  9. Boiling points of halogenated aliphatic compounds: a quantitative structure-property relationship for prediction and validation.

    PubMed

    Oberg, Tomas

    2004-01-01

    Halogenated aliphatic compounds have many technical uses, but substances within this group are also ubiquitous environmental pollutants that can affect the ozone layer and contribute to global warming. The establishment of quantitative structure-property relationships is of interest not only to fill in gaps in the available database but also to validate experimental data already acquired. The three-dimensional structures of 240 compounds were modeled with molecular mechanics prior to the generation of empirical descriptors. Two bilinear projection methods, principal component analysis (PCA) and partial-least-squares regression (PLSR), were used to identify outliers. PLSR was subsequently used to build a multivariate calibration model by extracting the latent variables that describe most of the covariation between the molecular structure and the boiling point. Boiling points were also estimated with an extension of the group contribution method of Stein and Brown.

  10. A complex interplay of three R2R3 MYB transcription factors determines the profile of aliphatic glucosinolates in Arabidopsis.

    PubMed

    Sønderby, Ida Elken; Burow, Meike; Rowe, Heather C; Kliebenstein, Daniel J; Halkier, Barbara Ann

    2010-05-01

    While R2R3 MYB transcription factors are a large gene family of transcription factors within plants, comprehensive functional data in planta are still scarce. A model for studying R2R3 MYB control of metabolic networks is the glucosinolates (GLSs), secondary metabolites that control plant resistance against insects and pathogens and carry cancer-preventive properties. Three related members of the R2R3 MYB transcription factor family within Arabidopsis (Arabidopsis thaliana), MYB28, MYB29, and MYB76, are the commonly defined regulators of aliphatic GLS biosynthesis. We utilized new genotypes and systems analysis techniques to test the existing regulatory model in which MYB28 is the dominant regulator, MYB29 plays a minor rheostat role, and MYB76 is largely uninvolved. We unequivocally show that MYB76 is not dependent on MYB28 and MYB29 for induction of aliphatic GLSs and that MYB76 plays a role in determining the spatial distribution of aliphatic GLSs within the leaf, pointing at a potential role of MYB76 in transport regulation. Transcriptional profiling of knockout mutants revealed that GLS metabolite levels are uncoupled from the level of transcript accumulation for aliphatic GLS biosynthetic genes. This uncoupling of chemotypes from biosynthetic transcripts suggests revising our view of the regulation of GLS metabolism from a simple linear transcription factor-promoter model to a more modular system in which transcription factors cause similar chemotypes via nonoverlapping regulatory patterns. Similar regulatory networks might exist in other secondary pathways.

  11. Asymmetric synthesis of bicyclic dihydropyrans via organocatalytic inverse-electron-demand oxo-Diels-Alder reactions of enolizable aliphatic aldehydes.

    PubMed

    Li, Jun-Long; Yang, Kai-Chuan; Li, Yi; Li, Qiang; Zhu, Hong-Ping; Han, Bo; Peng, Cheng; Zhi, Yong-Gang; Gou, Xiao-Jun

    2016-08-23

    A highly enantioselective organocatalytic inverse-electron-demand oxo-Diels-Alder reaction involving aqueous acetaldehyde has been discovered. The reaction, in which cyclic enones serve as dienes in the presence of readily available secondary amine catalysts, allows facile construction of optically active bicyclic dihydropyrans. Other typical enolizable aliphatic aldehydes can also serve as competent dienophiles in the reaction. PMID:27436351

  12. 40 CFR 721.3830 - Formaldehyde, reaction products with an alkylated phenol and an aliphatic amine (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Formaldehyde, reaction products with... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3830 Formaldehyde, reaction..., reaction products with an alkylated phenol and an aliphatic amine (PMN P-99-0531) is subject to...

  13. 40 CFR 721.3830 - Formaldehyde, reaction products with an alkylated phenol and an aliphatic amine (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Formaldehyde, reaction products with... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3830 Formaldehyde, reaction..., reaction products with an alkylated phenol and an aliphatic amine (PMN P-99-0531) is subject to...

  14. 40 CFR 721.3830 - Formaldehyde, reaction products with an alkylated phenol and an aliphatic amine (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Formaldehyde, reaction products with... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3830 Formaldehyde, reaction..., reaction products with an alkylated phenol and an aliphatic amine (PMN P-99-0531) is subject to...

  15. 40 CFR 721.3830 - Formaldehyde, reaction products with an alkylated phenol and an aliphatic amine (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Formaldehyde, reaction products with... CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.3830 Formaldehyde, reaction..., reaction products with an alkylated phenol and an aliphatic amine (PMN P-99-0531) is subject to...

  16. Liquid-phase synthesis of bridged peptides using olefin metathesis of a protected peptide with a long aliphatic chain anchor.

    PubMed

    Aihara, Keisuke; Komiya, Chiaki; Shigenaga, Akira; Inokuma, Tsubasa; Takahashi, Daisuke; Otaka, Akira

    2015-02-01

    Bridged peptides including stapled peptides are attractive tools for regulating protein-protein interactions (PPIs). An effective synthetic methodology in a heterogeneous system for the preparation of these peptides using olefin metathesis and hydrogenation of protected peptides with a long aliphatic chain anchor is reported. PMID:25629979

  17. Amperometric detection and electrochemical oxidation of aliphatic amines and ammonia on silver-lead oxide thin-film electrodes

    SciTech Connect

    Ge, Jisheng

    1996-01-08

    This thesis comprises three parts: Electrocatalysis of anodic oxygen-transfer reactions: aliphatic amines at mixed Ag-Pb oxide thin-film electrodes; oxidation of ammonia at anodized Ag-Pb eutectic alloy electrodes; and temperature effects on oxidation of ethylamine, alanine, and aquated ammonia.

  18. Liquid-phase synthesis of bridged peptides using olefin metathesis of a protected peptide with a long aliphatic chain anchor.

    PubMed

    Aihara, Keisuke; Komiya, Chiaki; Shigenaga, Akira; Inokuma, Tsubasa; Takahashi, Daisuke; Otaka, Akira

    2015-02-01

    Bridged peptides including stapled peptides are attractive tools for regulating protein-protein interactions (PPIs). An effective synthetic methodology in a heterogeneous system for the preparation of these peptides using olefin metathesis and hydrogenation of protected peptides with a long aliphatic chain anchor is reported.

  19. The impact of the absence of aliphatic glucosinolates on water transport under salt stress in Arabidopsis thaliana

    PubMed Central

    Martínez-Ballesta, Mcarmen; Moreno-Fernández, Diego A.; Castejón, Diego; Ochando, Cristina; Morandini, Piero A.; Carvajal, Micaela

    2015-01-01

    Members of the Brassicaceae are known for their contents of nutrients and health-promoting phytochemicals, including glucosinolates. Exposure to salinity increases the levels of several of these compounds, but their role in abiotic stress response is unclear. The effect of aliphatic glucosinolates on plant water balance and growth under salt stress, involving aquaporins, was investigated by means of Arabidopsis thaliana mutants impaired in aliphatic glucosinolate biosynthesis, which is controlled by two transcription factors: Myb28 and Myb29. The double mutant myb28myb29, completely lacking aliphatic glucosinolates, was compared to wild type Col-0 (WT) and the single mutant myb28. A greater reduction in the hydraulic conductivity of myb28myb29 was observed under salt stress, when compared to the WT and myb28; this correlated with the abundance of both PIP1 and PIP2 aquaporin subfamilies. Also, changes in root architecture in response to salinity were genotype dependent. Treatment with NaCl altered glucosinolates biosynthesis in a similar way in WT and the single mutant and differently in the double mutant. The results indicate that short-chain aliphatic glucosinolates may contribute to water saving under salt stress. PMID:26236322

  20. Aliphatic C-H to C-C Conversion: Synthesis of (−)-Cameroonan-7α-ol

    PubMed Central

    Taber, Douglass F.; Nelson, Christopher G.

    2011-01-01

    In the course of a synthesis of the tricyclic sesquiterpene (−)-cameroonan-7α-ol from the acyclic (+)-citronellal, seven aliphatic C-H bonds were converted to C-C bonds, and three rings and four new stereogenic centers were established. PMID:21344897