A systems biology approach identifies a R2R3 MYB gene subfamily with distinct and overlapping functions in regulation of aliphatic glucosinolates.

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Ida Elken Sønderby

Full Text Available BACKGROUND: Glucosinolates are natural metabolites in the order Brassicales that defend plants against both herbivores and pathogens and can attract specialized insects. Knowledge about the genes controlling glucosinolate regulation is limited. Here, we identify three R2R3 MYB transcription factors regulating aliphatic glucosinolate biosynthesis in Arabidopsis by combining several systems biology tools. METHODOLOGY/PRINCIPAL FINDINGS: MYB28 was identified as a candidate regulator of aliphatic glucosinolates based on its co-localization within a genomic region controlling variation both in aliphatic glucosinolate content (metabolite QTL and in transcript level for genes involved in the biosynthesis of aliphatic glucosinolates (expression QTL, as well as its co-expression with genes in aliphatic glucosinolate biosynthesis. A phylogenetic analysis with the R2R3 motif of MYB28 showed that it and two homologues, MYB29 and MYB76, were members of an Arabidopsis-specific clade that included three characterized regulators of indole glucosinolates. Over-expression of the individual MYB genes showed that they all had the capacity to increase the production of aliphatic glucosinolates in leaves and seeds and induce gene expression of aliphatic biosynthetic genes within leaves. Analysis of leaves and seeds of single knockout mutants showed that mutants of MYB29 and MYB76 have reductions in only short-chained aliphatic glucosinolates whereas a mutant in MYB28 has reductions in both short- and long-chained aliphatic glucosinolates. Furthermore, analysis of a double knockout in MYB28 and MYB29 identified an emergent property of the system since the absence of aliphatic glucosinolates in these plants could not be predicted by the chemotype of the single knockouts. CONCLUSIONS/SIGNIFICANCE: It seems that these cruciferous-specific MYB regulatory genes have evolved both overlapping and specific regulatory capacities. This provides a unique system within which to

Preparation and surface active properties of oxypropylated diol monoesters of fatty acids with an amide oxime terminal group

Directory of Open Access Journals (Sweden)

Eissa, A. M.F.

1994-10-01

Full Text Available Locally produced non-edible oil, namely, rice bran oil (R.B.O. was utilized as starting materials for preparing new nonionic surfactant. Oxypropylated diol monoesters of linoleic and rice bran oil fatty acids were prepared. Also amide oxime derivatives were obtained. Surface active properties of these compounds were measured. Under neutral condition amide eximes served as nonionic surfactants and their properties were similar to other oxypropylated monoesters.

Se ha utilizado un aceite no comestible de producción local, denominado, aceite de salvado de arroz (R.B.O. como materia prima para la preparación de nuevos tensioactivos no iónicos. Se prepararon diol monoésteres oxipropilados de ácido linoleico y ácidos grasos de aceite de salvado de arroz. También se obtuvieron los derivados de amido oxima. Se midieron las propiedades de tensión superficial de estos compuestos. Bajo condiciones neutras las amido eximas sirvieron como tensioactivos no iónicos y sus propiedades fueron similares a los de otros monoésteres oxipropilados.

Enhanced absorption and growth inhibition with amino acid monoester prodrugs of floxuridine by targeting hPEPT1 transporters.

Science.gov (United States)

Tsume, Yasuhiro; Vig, Balvinder S; Sun, Jing; Landowski, Christopher P; Hilfinger, John M; Ramachandran, Chandrasekharan; Amidon, Gordon L

2008-06-28

A series of amino acid monoester prodrugs of floxuridine was synthesized and evaluated for the improvement of oral bioavailability and the feasibility of target drug delivery via oligopeptide transporters. All floxuridine 5'-amino acid monoester prodrugs exhibited PEPT1 affinity, with inhibition coefficients of Gly-Sar uptake (IC50) ranging from 0.7 - 2.3 mM in Caco-2 and 2.0 - 4.8 mM in AsPC-1 cells, while that of floxuridine was 7.3 mM and 6.3 mM, respectively. Caco-2 membrane permeabilities of floxuridine prodrugs (1.01 - 5.31 x 10(-6 )cm/sec) and floxuridine (0.48 x 10(-6 )cm/sec) were much higher than that of 5-FU (0.038 x 10(-6) cm/sec). MDCK cells stably transfected with the human oligopeptide transporter PEPT1 (MDCK/hPEPT1) exhibited enhanced cell growth inhibition in the presence of the prodrugs. This prodrug strategy offers great potential, not only for increased drug absorption but also for improved tumor selectivity and drug efficacy.

Enhanced microemulsion formation in lipid-based drug delivery systems by combining mono-esters of mediumchain fatty acids with di- or tri-esters

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Darshil P. Patel

2012-06-01

Full Text Available To develop strategies for selecting appropriate lipids from mono-, di- and tri-esters of medium-chain fatty acids for the development of lipid-based drug delivery systems, ternary phase diagrams of propylene glycol (PG monocaprylate (Capryol® 90; HLB~7, PG dicaprylocaprate (Labrafac™ PG; HLB~2 and glycerol tricaprylocaprate (Labrafac™ Lipophile WL1349; HLB~2 were determined in combination with a common surfactant, PEG-35 castor oil (Cremophor® EL, HLB~13, and water. Particle size and viscosity in different regions of the phase diagrams were measured, solubility of a model drug, danazol, in different lipid-surfactant mixtures was determined, and dispersion testing by diluting selected preconcentrates with 250 ml 0.01 NHCl was performed. Further, phase diagrams were constructed using binary mixtures of lipids (monoester with diester, or monoester with triester in place of single lipids. The phase diagrams of PG dicaprylocaprate and glycerol tricaprylocaprate were similar, while it was distinctly different for PG monocaprylate. The microemulsion regions in phase diagrams were rather limited for individual lipids, and additionally, the diand tri-esters showed pronounced gel regions in the phase diagrams, which could influence drug release from preconcentrates. The mixing of PG monocaprylate (monoester with PG dicaprylocaprate (diester or glycerol tricaprylocaprate (triester had dramatic effects on the performance of lipids as evidenced by the greatly reduced gel phases, much larger microemulsion regions, faster dispersion of the preconcentrates in an aqueous medium, and smaller particle size of the microemulsions subsequently formed.

Negative ion electrospray ionization mass spectrometry of nucleoside phosphoramidate monoesters: elucidation of novel rearrangement mechanisms by multistage mass spectrometry incorporating in-source deuterium labelling.

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Xu, Peng-Xiang; Hu, An-Fu; Hu, Dan; Gao, Xiang; Zhao, Yu-Fen

2008-10-01

Several O-2',3'-isopropylideneuridine-O-5'-phosphoramidate monoesters were synthesized and analyzed by negative ion electrospray ionization tandem mass spectrometry (ESI-MS(n)). Two kinds of novel rearrangement reactions were observed due to the difference in the amino acid in the nucleoside phosphoramidate monoesters, and possible mechanisms were proposed. One involves a five-membered cyclic transition state. The other is formation of a stable five-membered ring intermediate by Michael addition. Results were confirmed by tandem mass spectrometry and isotopically labeled hydrogen atoms. Furthermore, the internal hydrogen exchange between active hydrogen and methyl acrylate in the heated capillary of the mass spectrometer was found. The characteristic fragmentation behavior in ESI-MS may be used to monitor this kind of compounds in the biological metabolism.

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

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aliphatic polycarboxylic acid metal... 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 this...

Determination of phthalate diesters and monoesters in human milk and infant formula by fat extraction, size-exclusion chromatography clean-up and gas chromatography-mass spectrometry detection.

Science.gov (United States)

Del Bubba, Massimo; Ancillotti, Claudia; Checchini, Leonardo; Fibbi, Donatella; Rossini, Daniele; Ciofi, Lorenzo; Rivoira, Luca; Profeti, Claudio; Orlandini, Serena; Furlanetto, Sandra

2018-01-30

A sensitive and reliable analytical method was developed for the simultaneous determination of five phthalate diesters and corresponding monoesters in human milk samples and infant formulas. The method involved a liquid-liquid extraction with a CH 2 Cl 2 /CH 3 OH/NaCl 30% 2/1/0.5 (v/v/v) mixture, the clean-up of the extract by size-exclusion chromatography (swelling and elution solvent: cyclohexane/ethyl acetate 9/1v/v), the derivatization of monoesters by trimethylsilyl-diazomethane and instrumental analysis by gas chromatography coupled with mass spectrometry. Recovery was in the range of 83-115% and precision was found between 9% and 21%. For phthalate diesters, method detection limits (MDLs) ranged from hundreds of ng/kg to 4.2μg/kg on a fresh weight milk (f.w.) basis, depending on blank contribution evaluated in matrix. Lower MDLs (0.03-0.8μg/kg f.w.) were achieved for corresponding monoesters. The proposed method was applied to the determination of target compounds in nine human milk samples and four infant formulas, confirming their presence in all samples. However, a generally higher contamination was assessed in artificial milk than in breast milk samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Structure and isotopic ratios of aliphatic side chains in the insoluble organic matter of the Murchison carbonaceous chondrite

Science.gov (United States)

Huang, Yongsong; Alexandre, Marcelo R.; Wang, Yi

2007-07-01

We report in this paper the first molecular and isotopic characterization of individual aliphatic side chains from the insoluble organic matter (IOM) in the Murchison carbonaceous chondrite using a novel combined approach of RuO 4 oxidation and solid phase microextraction (SPME). The aliphatic side chains in the IOM of Murchison were first released by oxidizing aromatic structures using RuO 4. Because the IOM of carbonaceous chondrites contains predominantly short (C 1 to C 9) aliphatic substitutions, the resulting low molecular weight monocarboxylic acids (MCAs) are highly volatile and water-soluble. The conventional aqueous extraction and derivatization procedures following RuO 4 oxidation are unable to recover MCAs for subsequent analyses. We overcame this problem by employing SPME to directly capture the MCAs from the aqueous solution. We selected a SPME fiber with greater affinity for longer chain monoacids to compensate for the exponential decline of monoacid concentrations with increasing carbon numbers in meteorite IOM, allowing more accurate identification and quantification for the less abundant monoacids. We also determined the carbon and hydrogen isotopic ratios of individual MCAs derived from Murchinson IOM. Our results reveal significant similarity in both molecular structures and hydrogen isotopic ratios between the IOM aliphatic side chains and water-soluble MCAs in Murchison, suggesting that these compounds had common precursors. Our combined new approach of RuO 4 oxidation-SPME provides a new way to probe the molecular and isotopic characteristics of aliphatic side chains in carbonaceous chondrites.

An approach towards understanding the structure of complex molecular systems: the case of lower aliphatic alcohols

Energy Technology Data Exchange (ETDEWEB)

Vrhovsek, Aleksander; Gereben, Orsolya; Pothoczki, Szilvia; Pusztai, Laszlo [Research Institute for Solid State Physics and Optics, Hungarian Academy of Sciences, H-1525 Budapest, PO Box 49 (Hungary); Tomsic, Matija; Jamnik, Andrej [Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, SI-1001 Ljubljana (Slovenia); Kohara, Shinji, E-mail: aleksander.vrhovsek@gmail.co [Research and Utilization Division, Japan Synchrotron Radiation Research Institute (JASRI, SPring-8), 1-1-1 Koto, Sayo-cho, Sayo-gun, Hyogo 679-5198 (Japan)

2010-10-13

An extensive study of liquid aliphatic alcohols methanol, ethanol, and propanol, applying reverse Monte Carlo modelling as a method of interpretation of diffraction data, is presented. The emphasis is on the evaluation of several computational strategies in view of their suitability to obtain high quality molecular models via the reverse Monte Carlo procedure. A consistent set of distances of closest approach and fixed neighbour constraints applicable to all three investigated systems was developed. An all-atom description is compared with a united-atom approach. The potentialities of employment of neutron diffraction data of completely deuterated and isotopically substituted samples, x-ray diffraction data, and results of either molecular dynamics or Monte Carlo calculations were investigated. Results show that parallel application of x-ray and neutron diffraction data, the latter being from completely deuterated samples, within an all-atom reverse Monte Carlo procedure is the most successful strategy towards attaining reliable, detailed, and well-structured molecular models, especially if the models are subsequently refined with the results of molecular dynamics simulations.

Enhanced Absorption and Growth Inhibition with Amino Acid Monoester Prodrugs of Floxuridine by Targeting hPEPT1 Transporters

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Gordon L. Amidon

2008-06-01

Full Text Available A series of amino acid monoester prodrugs of floxuridine was synthesized and evaluated for the improvement of oral bioavailability and the feasibility of target drug delivery via oligopeptide transporters. All floxuridine 5′-amino acid monoester prodrugs exhibited PEPT1 affinity, with inhibition coefficients of Gly-Sar uptake (IC50 ranging from 0.7 – 2.3 mM in Caco-2 and 2.0 – 4.8 mM in AsPC-1 cells, while that of floxuridine was 7.3 mM and 6.3 mM, respectively. Caco-2 membrane permeabilities of floxuridine prodrugs (1.01 – 5.31 x 10-6 cm/sec and floxuridine (0.48 x 10-6 cm/sec were much higher than that of 5-FU (0.038 x 10-6 cm/sec. MDCK cells stably transfected with the human oligopeptide transporter PEPT1 (MDCK/hPEPT1 exhibited enhanced cell growth inhibition in the presence of the prodrugs. This prodrug strategy offers great potential, not only for increased drug absorption but also for improved tumor selectivity and drug efficacy.

Effect of protonation on the mechanism of phosphate monoester hydrolysis and comparison with the hydrolysis of nucleoside triphosphate in biomolecular motors.

Science.gov (United States)

Hassan, Hammad Ali; Rani, Sadaf; Fatima, Tabeer; Kiani, Farooq Ahmad; Fischer, Stefan

2017-11-01

Hydrolysis of phosphate groups is a crucial reaction in living cells. It involves the breaking of two strong bonds, i.e. the O a H bond of the attacking water molecule, and the PO l bond of the substrate (O a and O l stand for attacking and leaving oxygen atoms). Mechanism of the hydrolysis reaction can proceed either by a concurrent or a sequential mechanism. In the concurrent mechanism, the breaking of O a H and PO l bonds occurs simultaneously, whereas in the sequential mechanism, the O a H and PO l bonds break at different stages of the reaction. To understand how protonation affects the mechanism of hydrolysis of phosphate monoester, we have studied the mechanism of hydrolysis of protonated and deprotonated phosphate monoester at M06-2X/6-311+G**//M06-2X/6-31+G*+ZPE level of theory (where ZPE stands for zero point energy). Our calculations show that in both protonated and deprotonated cases, the breaking of the water O a H bond occurs before the breaking of the PO l bond. Because the two events are not separated by a stable intermediate, the mechanism can be categorized as semi-concurrent. The overall energy barrier is 41kcalmol -1 in the unprotonated case. Most (5/6th) of this is due to the initial breaking of the water O a H bond. This component is lowered from 34 to 25kcalmol -1 by adding one proton to the phosphate. The rest of the overall energy barrier comes from the subsequent breaking of the PO l bond and is not sensitive to protonation. This is consistent with previous findings about the effect of triphosphate protonation on the hydrolysis, where the equivalent protonation (on the γ-phosphate) was seen to lower the barrier of breaking the water O a H bond and to have little effect on the PO l bond breaking. Hydrolysis pathways of phosphate monoester with initial breaking of the PO l bond could not be found here. This is because the leaving group in phosphate monoester cannot be protonated, unlike in triphosphate hydrolysis, where protonation of the �

Non-hazardous organic solvents in the paraffin-embedding technique

DEFF Research Database (Denmark)

Holm, Inger Lindebo; Lyon, Hans; Prentø, Poul

1995-01-01

The aim of this study was to substitute hazardous compounds, used in tissue processing and dewaxing, with compounds having lowest possible toxicity and inflammability without impairing the morphology, staining characteristics, or diagnostic value of the tissue sections. All aromatic compounds...... and aliphatic hydrocarbons (e.g. alkanes, isoparaffins, petroleum distillates, etc.) were rejected, primarily due to their high vapour pressure. Based on a theoretical study of compounds used for clearing, a number of non-hazardous potential substitutes were chosen. The following experimental study narrowed...... the group to three unbranched, saturated, aliphatic monoesters containing 12-14 carbon atoms. On large-scale testing of these compounds, we found butyldecanoate to be the closest to an ideal substitute for aromatic and aliphatic hydrocarbons in the histology department: the section quality is at least equal...

Aliphatic alcohols in spirits inhibit phagocytosis by human monocytes.

Science.gov (United States)

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.

Chemistry of aliphatic sulfurpentafluoride derivatives

International Nuclear Information System (INIS)

Bissell, E.R.

1975-01-01

This report summarizes the literature through 1974 on aliphatic sulfurpentafluoride compounds. Methods of preparation and methods of transforming one pentafluorothio compound into another are briefly discussed. The physical properties of all known derivatives are tabulated

Aliphatic isocyanurates and polyisocyanurate networks

NARCIS (Netherlands)

Driest, Pieter Job; Lenzi, V.; Marques, L.S.A.; Ramos, M.M.D; Dijkstra, D.J.; Richter, F.U.; Stamatialis, Dimitrios; Grijpma, Dirk W.

2016-01-01

The production, processing, and application of aliphatic isocyanate (NCO)-based thermosets such as polyurethane coatings and adhesives are generally limited by the surprisingly high viscosity of tri-functionality and higher-functionality isocyanurates. These compounds are essential crosslinking

Aliphatic isocyanurates and polyisocyanurate networks

NARCIS (Netherlands)

Driest, P. J.; Lenzi, V.; Marques, L. S. A.; Ramos, M. M. D.; Dijkstra, D. J.; Richter, F. U.; Stamatialis, D.; Grijpma, D. W.

2017-01-01

The production, processing, and application of aliphatic isocyanate (NCO)-based thermosets such as polyurethane coatings and adhesives are generally limited by the surprisingly high viscosity of tri-functionality and higher-functionality isocyanurates. These compounds are essential crosslinking

Fate of aliphatic compounds in nitric acid processing solutions

International Nuclear Information System (INIS)

Clark, W.E.; Howerton, W.B.

1975-01-01

The reaction of hyperazeotropic iodic acid-saturated nitric acid with short chain aliphatic iodides, nitrates, and acids was studied in order to determine the conditions for complete removal of organic materials from nitric acid systems. The aliphatic iodides are converted to the nitrates and the nitrates in strong HNO 3 are extensively converted into CO 2 and acids. The aliphatic acids are rather stable; acetic acid was unattacked by boiling in 20M HNO 3 and n-butyric acid was 80 percent unattacked. The dibasic acids oxalic and malonic are extensively attacked, but succinic acid is relatively stable. A wet oxidation method is successful in destroying acetic acid in 5 to 8M HNO 3 . (U.S.)

Combinations of Aromatic and Aliphatic Radiolysis.

Science.gov (United States)

LaVerne, Jay A; Dowling-Medley, Jennifer

2015-10-08

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.

Aliphatic alkenes and alkynes

International Nuclear Information System (INIS)

Serep, D.

1985-01-01

Papers on radiolysis of aliphatic alkenes and alkynes published after 1968 are analytically reviewed. Kinetics and mechanisms of radiolytic processes, dependences of yields of intermediate and final products on conditions of their procedure and molecular structure of compounds are considered. Certain attention is paid to problems of dimerization and oligomerization at radiolysis of the considered compounds

Nickel-catalysed retro-hydroamidocarbonylation of aliphatic amides to olefins

Science.gov (United States)

Hu, Jiefeng; Wang, Minyan; Pu, Xinghui; Shi, Zhuangzhi

2017-05-01

Amide and olefins are important synthetic intermediates with complementary reactivity which play a key role in the construction of natural products, pharmaceuticals and manmade materials. Converting the normally highly stable aliphatic amides into olefins directly is a challenging task. Here we show that a Ni/NHC-catalytic system has been established for decarbonylative elimination of aliphatic amides to generate various olefins via C-N and C-C bond cleavage. This study not only overcomes the acyl C-N bond activation in aliphatic amides, but also encompasses distinct chemical advances on a new type of elimination reaction called retro-hydroamidocarbonylation. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for late-stage olefination of amide groups in complex compounds.

Natural attenuation of diesel aliphatic hydrocarbons in contaminated agricultural soil

International Nuclear Information System (INIS)

Serrano, Antonio; Gallego, Mercedes; Gonzalez, Jose Luis; Tejada, Manuel

2008-01-01

A diesel fuel spill at a concentration of 1 L m -2 soil was simulated on a 12 m 2 plot of agricultural land, and natural attenuation of aliphatic hydrocarbons was monitored over a period of 400 days following the spill after which the aliphatic hydrocarbon concentrations were found to be below the legal contamination threshold for soil. The main fraction of these compounds (95%) remained at the surface layer (0-10 cm). Shortly after the spill (viz. between days 0 and 18), evaporation was the main origin of the dramatic decrease in pollutant concentrations in the soil. Thereafter, soil microorganisms used aliphatic hydrocarbons as sources of carbon and energy, as confirmed by the degradation ratios found. Soil quality indicators, soil microbial biomass and dehydrogenase activity, regained their original levels about 200 days after the spill. - The effect of aliphatic hydrocarbons contamination on soil quality was monitored over a period of 400 days after a Diesel fuel spill

Differentiation between lutein monoester regioisomers and detection of lutein diesters from marigold flowers (Tagetes erecta L.) and several fruits by liquid chromatography-mass spectrometry.

Science.gov (United States)

Breithaupt, Dietmar E; Wirt, Ursula; Bamedi, Ameneh

2002-01-02

Liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCIMS) was employed for the identification of eight lutein monoesters, formed by incomplete enzymatic saponification of lutein diesters of marigold (Tagetes erecta L.) by Candida rugosa lipase. Additionally, the main lutein diesters naturally occurring in marigold oleoresin were chromatographically separated and identified. The LC-MS method allows for characterization of lutein diesters occurring as minor components in several fruits; this was demonstrated by analysis of extracts of cape gooseberry (Physalis peruviana L.), kiwano (Cucumis metuliferus E. Mey. ex Naud.), and pumpkin (Cucurbita pepo L.). The assignment of the regioisomers of lutein monoesters is based on the characteristic fragmentation pattern: the most intense daughter ion generally results from the loss of the substituent (fatty acid or hydroxyl group) bound to the epsilon-ionone ring, yielding an allylic cation. The limit of detection was estimated at 0.5 microg/mL with lutein dimyristate as reference compound. This method provides a useful tool to obtain further insight into the biochemical reactions leading to lutein ester formation in plants.

Estimates of Gibbs free energies of formation of chlorinated aliphatic compounds

NARCIS (Netherlands)

Dolfing, Jan; Janssen, Dick B.

1994-01-01

The Gibbs free energy of formation of chlorinated aliphatic compounds was estimated with Mavrovouniotis' group contribution method. The group contribution of chlorine was estimated from the scarce data available on chlorinated aliphatics in the literature, and found to vary somewhat according to the

Microwave-assisted nonionic surfactant extraction of aliphatic hydrocarbons from petroleum source rock

Energy Technology Data Exchange (ETDEWEB)

Akinlua, A., E-mail: geochemresearch@yahoo.com [Fossil Fuels and Environmental Geochemistry Group, Department of Chemistry, Obafemi Awolowo University, Ile-Ife (Nigeria); Jochmann, M.A.; Laaks, J.; Ewert, A.; Schmidt, T.C. [Instrumental Analytical Chemistry, University Duisburg-Essen, Universitaetsstr, 5, 45141 Essen (Germany)

2011-04-08

The extraction of aliphatic hydrocarbons from petroleum source rock using nonionic surfactants with the assistance of microwave was investigated and the conditions for maximum yield were determined. The results showed that the extraction temperatures and kinetic rates have significant effects on extraction yields of aliphatic hydrocarbons. The optimum temperature for microwave-assisted nonionic surfactant extraction of aliphatic hydrocarbons from petroleum source rock was 105 deg. C. The optimum extraction time for the aliphatic hydrocarbons was at 50 min. Concentration of the nonionic surfactant solution and irradiation power had significant effect on the yields of aliphatic hydrocarbons. The yields of the analytes were much higher using microwave assisted nonionic surfactant extraction than with Soxhlet extraction. The recoveries of the n-alkanes and acyclic isoprenoid hydrocarbons for GC-MS analysis from the extractant nonionic surfactant solution by in-tube extraction (ITEX 2) with a TENAX TA adsorbent were found to be efficient. The results show that microwave-assisted nonionic surfactant extraction (MANSE) is a good and efficient green analytical preparatory technique for geochemical evaluation of petroleum source rock.

Microwave-assisted nonionic surfactant extraction of aliphatic hydrocarbons from petroleum source rock

International Nuclear Information System (INIS)

Akinlua, A.; Jochmann, M.A.; Laaks, J.; Ewert, A.; Schmidt, T.C.

2011-01-01

The extraction of aliphatic hydrocarbons from petroleum source rock using nonionic surfactants with the assistance of microwave was investigated and the conditions for maximum yield were determined. The results showed that the extraction temperatures and kinetic rates have significant effects on extraction yields of aliphatic hydrocarbons. The optimum temperature for microwave-assisted nonionic surfactant extraction of aliphatic hydrocarbons from petroleum source rock was 105 deg. C. The optimum extraction time for the aliphatic hydrocarbons was at 50 min. Concentration of the nonionic surfactant solution and irradiation power had significant effect on the yields of aliphatic hydrocarbons. The yields of the analytes were much higher using microwave assisted nonionic surfactant extraction than with Soxhlet extraction. The recoveries of the n-alkanes and acyclic isoprenoid hydrocarbons for GC-MS analysis from the extractant nonionic surfactant solution by in-tube extraction (ITEX 2) with a TENAX TA adsorbent were found to be efficient. The results show that microwave-assisted nonionic surfactant extraction (MANSE) is a good and efficient green analytical preparatory technique for geochemical evaluation of petroleum source rock.

Urinary phthalate monoesters and endometriosis in infertile Japanese women

International Nuclear Information System (INIS)

Itoh, Hiroaki; Iwasaki, Motoki; Hanaoka, Tomoyuki; Sasaki, Hiroshi; Tanaka, Tadao; Tsugane, Shoichiro

2009-01-01

Phthalates may act as an estrogen and are a potential risk factor for estrogen-related diseases such as endometriosis. We assessed the association between phthalate exposure and endometriosis in 166 consecutive women who presented at a university hospital for consultation regarding infertility. The subjects were interviewed and provided a urine specimen prior to a laparoscopic diagnosis of endometriosis. They were then categorized by the severity of endometriosis as controls (stages 0-I) and cases (stages II-IV). Urinary concentrations of the phthalate metabolites monoethyl phthalate, mono-n-butyl phthalate, monobenzyl phthalate, mono(2-ethylhexyl) phthalate (MEHP), mono(2-ethyl-5-oxohexyl) phthalate, and mono(2-ethyl-5-hydroxyhexyl) phthalate were measured in 57 cases and 80 controls using high-performance liquid chromatography isotope-dilution tandem mass spectrometry. Adjusted odds ratios for endometriosis in relation to dichotomized individual phthalate metabolites (standardized for creatinine) were calculated. No significant association between endometriosis and any urinary creatinine-adjusted phthalate monoester was seen. Adjusted odds ratio (95% confidence interval) for higher dichotomized MEHP by endometriosis was 1.57 (0.74-3.30). No monotonic trend was seen in urinary creatinine-adjusted concentration of phthalate metabolites by endometriosis stage (p = 0.23-0.90). Our results do not support the hypothesis that higher urinary concentrations of phthalate metabolites are associated with the risk of endometriosis in infertile Japanese women.

Urinary phthalate monoesters and endometriosis in infertile Japanese women

Energy Technology Data Exchange (ETDEWEB)

Itoh, Hiroaki [Epidemiology and Prevention Division, Research Center for Cancer Prevention and Screening, National Cancer Center, 5-1-1 Tsukiji, Chuo-ku, Tokyo 104-0045 (Japan); Iwasaki, Motoki, E-mail: moiwasak@ncc.go.jp [Epidemiology and Prevention Division, Research Center for Cancer Prevention and Screening, National Cancer Center, 5-1-1 Tsukiji, Chuo-ku, Tokyo 104-0045 (Japan); Hanaoka, Tomoyuki [Epidemiology and Prevention Division, Research Center for Cancer Prevention and Screening, National Cancer Center, 5-1-1 Tsukiji, Chuo-ku, Tokyo 104-0045 (Japan); Sasaki, Hiroshi; Tanaka, Tadao [Department of Obstetrics and Gynecology, Jikei University School of Medicine, 3-25-8, Nishi-Shimbashi, Minato-ku, Tokyo 105-8461 (Japan); Tsugane, Shoichiro [Epidemiology and Prevention Division, Research Center for Cancer Prevention and Screening, National Cancer Center, 5-1-1 Tsukiji, Chuo-ku, Tokyo 104-0045 (Japan)

2009-12-15

Phthalates may act as an estrogen and are a potential risk factor for estrogen-related diseases such as endometriosis. We assessed the association between phthalate exposure and endometriosis in 166 consecutive women who presented at a university hospital for consultation regarding infertility. The subjects were interviewed and provided a urine specimen prior to a laparoscopic diagnosis of endometriosis. They were then categorized by the severity of endometriosis as controls (stages 0-I) and cases (stages II-IV). Urinary concentrations of the phthalate metabolites monoethyl phthalate, mono-n-butyl phthalate, monobenzyl phthalate, mono(2-ethylhexyl) phthalate (MEHP), mono(2-ethyl-5-oxohexyl) phthalate, and mono(2-ethyl-5-hydroxyhexyl) phthalate were measured in 57 cases and 80 controls using high-performance liquid chromatography isotope-dilution tandem mass spectrometry. Adjusted odds ratios for endometriosis in relation to dichotomized individual phthalate metabolites (standardized for creatinine) were calculated. No significant association between endometriosis and any urinary creatinine-adjusted phthalate monoester was seen. Adjusted odds ratio (95% confidence interval) for higher dichotomized MEHP by endometriosis was 1.57 (0.74-3.30). No monotonic trend was seen in urinary creatinine-adjusted concentration of phthalate metabolites by endometriosis stage (p = 0.23-0.90). Our results do not support the hypothesis that higher urinary concentrations of phthalate metabolites are associated with the risk of endometriosis in infertile Japanese women.

Synthesis of novel naphthoquinone aliphatic amides and esters and their anticancer evaluation.

Science.gov (United States)

Kongkathip, Boonsong; Akkarasamiyo, Sunisa; Hasitapan, Komkrit; Sittikul, Pichamon; Boonyalai, Nonlawat; Kongkathip, Ngampong

2013-02-01

Fourteen new naphthoquinone aliphatic amides and seventeen naphthoquinone aliphatic esters were synthesized in nine to ten steps from 1-hydroxy-2-naphthoic acid with 9-25% overall yield for the amides, and 16-21% overall yield for the esters. The key step of the amide synthesis is a coupling reaction between amine and various aliphatic acids using 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM) as a coupling agent while for the ester synthesis, DCC/DMAP or CDI was used as the coupling reagent between aliphatic acids and naphthoquinone alcohol. Both naphthoquinone amides and esters were evaluated for their anticancer activity against KB cells. It was found that naphthoquinone aliphatic amides showed stronger anticancer activity than those of the esters when the chains are longer than 7-carbon atoms. The optimum chain of amides is expected to be 16-carbon atoms. In addition, naphthoquinone aliphatic esters with α-methyl on the ester moiety possessed much stronger anticancer activity than the straight chains. Decatenation assay revealed that naphthoquinone amide with 16-carbon atoms chain at 15 μM and 20 μM can completely inhibit hTopoIIα activity while at 10 μM the enzyme activity was moderately inhibited. Molecular docking result also showed the same trend as the cytotoxicity and decatenation assay. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

The influence of aliphatic side chain of anacardic acid on molecular ...

African Journals Online (AJOL)

Interestingly, the presence of the aliphatic side chain in AnMcr resulted in more uniform imprinted beads as compared to particle agglomerates obtained from SaMcr in the presence of propranolol template. Therefore, the aliphatic side chain of anacardic acid improves both molecular recognition of imprinted polymers as ...

Substrate specific hydrolysis of aromatic and aromatic-aliphatic esters in orchid tissue cultures

Directory of Open Access Journals (Sweden)

Agnieszka Mironowicz

2014-01-01

Full Text Available We found that tissue cultures of higher plants were able, similarly as microorganisms, to transform low-molecular-weight chemical compounds. In tissue cultures of orchids (Cymbidium 'Saint Pierre' and Dendrobium phalaenopsis acetates of phenols and aromatic-aliphatic alcohols were hydrolyzed, whereas methyl esters of aromatic and aromatic-aliphatic acids did not undergo this reaction. Acetates of racemic aromatic-aliphatic alcohols were hydrolyzed with distinct enantiospecificity.

Vapor pressure and enthalpy of vaporization of aliphatic propanediamines

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Chernyak, Yury

2012-01-01

Highlights: ► We measured vapor pressure of four aliphatic 1,3-diamines. ► Vaporization enthalpies at 298 K were derived. ► We examined consistency of new and available data in the literature. ► A group-contribution method for prediction was developed. - Abstract: Vapor pressures of four aliphatic propanediamines including N-methyl-1,3-propanediamine (MPDA), N,N-dimethyl-1,3-propanediamine (DMPDA), N,N-diethyl-1,3-propanediamine (DEPDA) and N,N,N′,N′-tetramethyl-1,3-propanediamine (4MPDA) were measured using the transpiration method. The vapor pressures developed in this work and reported in the literature were used to derive molar enthalpy of vaporization values at the reference temperature 298.15 K. An internal consistency check of the enthalpy of vaporization was performed for the aliphatic propanediamines studied in this work. A group-contribution method was developed for the validation and prediction vaporization enthalpies of amines and diamines.

Aliphatic hydrocarbons in surface sediments from South China Sea off Kuching Division, Sarawak

International Nuclear Information System (INIS)

Hafidz Yusoff; Zaini Assim; Samsur Mohamad

2012-01-01

Eighteen surface sediment samples collected from South China Sea off Kuching Division, Sarawak were analyzed for aliphatic hydrocarbons. These hydrocarbons were recovered from sediment by Soxhlet extraction method and then analyzed using gas chromatography equipped with mass spectrometer (GC/ MS). Total concentrations of aliphatic hydrocarbons in surface sediments from South China Sea off Kuching division are ranged from 35.6 μg/ g to 1466.1 μg/ g dry weights. The sediments collected from Bako Bay, Kuching showed high concentrations of total aliphatic hydrocarbons. Several molecular indices were used to predict the predominant sources of hydrocarbons. Carbon preference index (CPI) value revealed widespread anthropogenic input in this study area (CPI= 0 to 4.1). The ratio of C 31 / C 19 and C 29 / C 31 indicated that major input of aliphatic hydrocarbon mostly transfer by lateral input to the marine environment than atmospheric movements. Generally, the concentrations of aliphatic hydrocarbons in sediment from South China Sea off Kuching division are generally higher compare to other area in the world. (author)

Synthesis and pharmacological activity evaluation of arctigenin monoester derivatives.

Science.gov (United States)

Chen, Qiulian; Yang, Limin; Han, Mei; Cai, Enbo; Zhao, Yan

2016-12-01

Arctigenin (ARG), a nature medicine with many pharmacological activities, was poorly soluble in water and placed restriction on practical usage. Six novel arctigenin monoester derivatives were obtained from the reflux reaction with arctigenin, carboxylic acids (crotonic acid, furoic acid, 2-naphthalene acid and indol-3-acetic acid), EDCI and DMAP in dichloromethane at 60°C for 4-6h and their properties on nitrite scavenging assay were investigated in vitro. Based on the results, the one of the most effective derivatives, arctigenin β-indolylacetate (ARG6), was selected to study anti-tumor activity in vivo at doses of 20 and 40mg/kg. The results showed that comparison with ARG group, ARG6 exhibited more anti-tumor activity in H22 tumor-bearing mice. Furthermore, ARG6 exhibited less damage to the liver, kidney, spleen and thymus when compared with those in positive group. Biochemical parameters of ALT, AST, BUN and Cre showed ARG6 had little toxicity to mice as well. ARG6 significantly improved serum cytokine levels of IL-2, IL-6, IFN-γ and TNF-α, and decreased VEGF compared with ARG. Moreover, H & E staining, TUNEL assay and immunohistochemical of tumor issues also indicated that ARG6 exhibited anti-tumor activity in vivo. In brief, the present study provide a method to improve ARG anti-tumor activity and provide a reference for new anti-tumor agent. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

Science.gov (United States)

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.

Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

International Nuclear Information System (INIS)

Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F.

2013-01-01

Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

Iodine - catalyzed prins cyclization of aliphatic and aromatic ketones

Energy Technology Data Exchange (ETDEWEB)

Kishore, K.R.; Reddy, K.; Silva Junior, Luiz F., E-mail: luizfsjr@iq.usp.br [Universidade de Sao Paulo (IQ/USP), SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental

2013-09-15

Iodine-catalyzed Prins cyclization of homoallylic alcohols and ketones was investigated. Anhydrous conditions and inert atmosphere are not required in this metal-free protocol. The reaction of 2-(3,4-dihydronaphthalene-1-yl)propan-1-ol with six aliphatic symmetric ketones gave the desired products in 67-77% yield. Cyclization was performed with four aliphatic unsymmetric ketones, leading to corresponding pyrans in 66-76% yield. Prins cyclization was also accomplished with four aromatic ketones in 37-66% yield. Finally, Prins cyclization of the monoterpene isopulegol and acetone was successfully achieved. (author)

Rigid particle toughening of aliphatic polyketone

NARCIS (Netherlands)

Zuiderduin, W.C.J.; Huetink, Han; Gaymans, R.J.

2006-01-01

The influence of precipitated calcium carbonate particles on the toughening behaviour of aliphatic polyketone has been studied. The calcium carbonate particles had a particle size of 0.7 mm and a stearic acid coating (1%). Composites of 0e31.5 vol% CaCO3 content have been compounded and injection

Notch sensitivity of aliphatic polyketone terpolymers

NARCIS (Netherlands)

Zuiderduin, W.C.J.; Huetink, Han; Gaymans, R.J.

2004-01-01

The notch sensitivity of aliphatic polyketone (PK) terpolymers was investigated in this article. The notch-tip radius was varied between the size of an actual propagating crack tip of 1-2 m and the largest notch tip of 1000 m radius. The larger notch-tip radii (1000-15 m) were milled into the

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

Science.gov (United States)

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.

Biodegradation of aliphatic vs. aromatic hydrocarbons in fertilized arctic soils

Science.gov (United States)

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.

Facile synthesis of aliphatic isothiocyanates and thioureas on solid phase using peptide coupling reagents

DEFF Research Database (Denmark)

Boas, Ulrik; Andersen, Heidi Gertz; Christensen, Jørn B.

2004-01-01

Peptide coupling reagents can be used as versatile reagents for the formation of aliphatic isothiocyanates and thioureas on solid phase from the corresponding solid-phase anchored aliphatic primary amines. The formation of the thioureas is fast and highly chemoselective, and proceeds via formatio...

Kinetic analysis of the reactivity of aliphatic cyclic alcohols and carboxylic acids in the T-for-H exchange reaction

International Nuclear Information System (INIS)

Tamura, Kiyoshi; Imaizumi, Hiroshi; Kano, Naoki

2007-01-01

In order to quantitatively evaluate the influence of tritium ( 3 He or T) on various functional groups in environment, the hydrogen isotope exchange reaction (T-for-H exchange reaction) between tritium-labeled poly-(vinyl alcohol) and each aliphatic cyclic alcohol (or carboxylic acid) has been dynamically observed in the range of 50 to 90degC. Consequently, the activities of the aliphatic cyclic alcohol and carboxylic acid increased with increasing reaction time. Applying in A''-McKay plot method to the observed data, the rate constants (k) for these materials were obtained. Using the k, the relation between the number of carbon atoms in the ring in each alcohol and the reactivity of the alcohol was quantitatively compared. Then, to clarify the effect of relative atomic charge of O atom (connected with the H atom in the hydroxy (or carboxy) group in the material) on the reactivity of the material, the MOPAC method was used. From both the above-mentioned and the obtained previously, the following nine items were found as to aliphatic cyclic alcohols (and carboxylic acids) in the T-for-H exchange reaction. (1) The reactivity of aliphatic cyclic alcohols (and carboxylic acids) depends on the temperature. (2) The reactivity of the cyclic materials decreases with increasing number of carbon atoms in the ring. (3) The reactivity of the aliphatic cyclic carboxylic acid seems to be smaller than that of aliphatic cyclic alcohol, and be larger than that of aliphatic cyclic amine. (4) For aliphatic cyclic alcohols, correlation exists between k and relative atomic charges of O atom obtained by the MOPAC method, but the tendency for aliphatic cyclic carboxylic acid is not clear. (5) As to having the same number of carbon atoms in each ring, the reactivity of the aliphatic cyclic carboxylic acid including the side chain is smaller than of the aliphatic cyclic carboxylic acid including no side chain. (6) The reactivity of aliphatic cyclic carboxylic acid is larger than that of

Chemical modifications and applications of alternating aliphatic polyketones

NARCIS (Netherlands)

Zhang, Youchun

2008-01-01

Alternating aliphatic polyketones, produced by co- and terpolymerization of carbon monoxide and olefins (mixtures of ethylene and propylene) using palladium-based homogeneous catalysis represent a very promising class of polymers for a wide range of applications. Besides many interesting chemical

Cyano-containing ionic liquids for the extraction of aromatic hydrocarbons from an aromatic/aliphatic mixture

NARCIS (Netherlands)

Meindersma, G.W.; Haan, de A.B.

2012-01-01

Ionic liquids can replace conventional solvents in aromatic/aliphatic extractions, if they have higher aromatic distribution coefficients and higher or similar aromatic/aliphatic selectivities. Also physical properties, such as density and viscosity, must be taken into account if a solvent is

Nano-biocomposites based on synthetic aliphatic polyesters and nanoclay

CSIR Research Space (South Africa)

Ojijo, Vincent O

2014-05-01

Full Text Available This article gives an overview of the recent developments in the preparation, characterisation, properties, crystallisation behaviour, and melt rheology of clay-containing composites of biodegradable synthetic aliphatic polyesters such as poly...

Prediction of anticancer activity of aliphatic nitrosoureas using ...

African Journals Online (AJOL)

Design and development of new anticancer drugs with low toxicity is a very challenging task and computer aided methods are being increasingly used to solve this problem. In this study, we investigated the anticancer activity of aliphatic nitrosoureas using quantum chemical quantitative structure activity relation (QSAR) ...

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

Science.gov (United States)

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.

Inhibition of Tetrahymena pyriformis growth by Aliphatic Alcohols ...

African Journals Online (AJOL)

A Quantitative Structure- Activity Relationship (QSAR) study was undertaken to evaluate the relative toxicity of a mixed series of 21 (linear and branched-chain) alcohols and 9 normal aliphatic amines in term of the 50% inhibitory growth concentration (IGC50) of Tetrahymena pyriformis. The applied simple linear regression ...

Potential Development of Tumor-Targeted Oral Anti-Cancer Prodrugs: Amino Acid and Dipeptide Monoester Prodrugs of Gemcitabine.

Science.gov (United States)

Tsume, Yasuhiro; Drelich, Adam J; Smith, David E; Amidon, Gordon L

2017-08-10

One of the main obstacles for cancer therapies is to deliver medicines effectively to target sites. Since stroma cells are developed around tumors, chemotherapeutic agents have to go through stroma cells in order to reach tumors. As a method to improve drug delivery to the tumor site, a prodrug approach for gemcitabine was adopted. Amino acid and dipeptide monoester prodrugs of gemcitabine were synthesized and their chemical stability in buffers, resistance to thymidine phosphorylase and cytidine deaminase, antiproliferative activity, and uptake/permeability in HFF cells as a surrogate to stroma cells were determined and compared to their parent drug, gemcitabine. The activation of all gemcitabine prodrugs was faster in pancreatic cell homogenates than their hydrolysis in buffer, suggesting enzymatic action. All prodrugs exhibited great stability in HFF cell homogenate, enhanced resistance to glycosidic bond metabolism by thymidine phosphorylase, and deamination by cytidine deaminase compared to their parent drug. All gemcitabine prodrugs exhibited higher uptake in HFF cells and better permeability across HFF monolayers than gemcitabine, suggesting a better delivery to tumor sites. Cell antiproliferative assays in Panc-1 and Capan-2 pancreatic ductal cell lines indicated that the gemcitabine prodrugs were more potent than their parent drug gemcitabine. The transport and enzymatic profiles of gemcitabine prodrugs suggest their potential for delayed enzymatic bioconversion and enhanced resistance to metabolic enzymes, as well as for enhanced drug delivery to tumor sites, and cytotoxic activity in cancer cells. These attributes would facilitate the prolonged systemic circulation and improved therapeutic efficacy of gemcitabine prodrugs.

Electrooxidation of aliphatic alcohols on palladium oxide catalyst prepared by pulsed electrodeposition technique

International Nuclear Information System (INIS)

Casella, Innocenzo G.

2009-01-01

Palladium film can be deposited on gold polycrystalline electrodes, from a deoxygenated alkaline solution containing 50 mM NaOH plus 0.5 mM K 2 Pd(CN) 4 . A multipulse sequence of potentials of equal amplitude and duration was used for the palladium deposition process. In particular, an optimized waveform of potentials of E 1 = 1.0 V vs. SCE and E 2 = -1.0 V vs. SCE for the relevant pulse duration of t 1 = 0.05 s and t 2 = 0.05 s, for 30 s, was used. Cyclic voltammetry and scanning electron microscopy (SEM) were employed to characterize the gold-palladium modified electrode (Au-Pd) towards the electrooxidation of aliphatic alcohols in alkaline solutions. The voltammetric study suggests that the kinetics involved in the alcohol electrooxidation at the Pd-Au electrode are sensibly higher than those observed on the bare Pd and Au electrodes. In addition, the most interesting aspect of the electrooxidation of aliphatic alcohols at the Au-Pd electrode was that as the number of methylene groups on the homologous series of aliphatic alcohols increased, the molar response also increased. Under pulsed chronoamerometric conditions (PCC), using an optimized triple pulse waveform of potentials the modified electrode exhibits interesting catalytic currents without any apparent poisoning effects during the oxidation of aliphatic alcohols.

Cloud condensation nuclei activity of aliphatic amine secondary aerosol

Science.gov (United States)

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 ...

Structure and properties of porous films based on aliphatic copolyamide developed for cellular technologies

Czech Academy of Sciences Publication Activity Database

Dobrovol`skaya, I.P.; Popryadukhin, P.V.; Yudin, V. E.; Ivankova, E.M.; Elokhovskiy, V.Y.; Weishauptová, Zuzana; Balík, Karel

2015-01-01

Roč. 26, č. 1 (2015), article number 46 ISSN 0957-4530 Institutional support: RVO:67985891 Keywords : porous film * aliphatic copolyamide * structure * properties Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.272, year: 2015 http://www.stem-art.com/Library/Science/Structure%20and%20properties%20of%20porous%20films%20based%20on%20aliphatic%20copolyamide%20developed%20for%20cellular%20technologies.pdf

Molecular Characterization of MYB28 Involved in Aliphatic Glucosinolate Biosynthesis in Chinese Kale (Brassica oleracea var. alboglabra Bailey

Directory of Open Access Journals (Sweden)

Ling Yin

2017-06-01

Full Text Available Glucosinolates are Brassicaceae-specific secondary metabolites that act as crop protectants, flavor precursors, and cancer-prevention agents, which shows strong evidences of anticarcinogentic, antioxidant, and antimicrobial activities. MYB28, the R2R3-MYB28 transcription factor, directly activates genes involved in aliphatic glucosinolate biosynthesis. In this study, the MYB28 homology (BoaMYB28 was identified in Chinese kale (Brassica oleracea var. alboglabra Bailey. Analysis of the nucleotide sequence indicated that the cDNA of BoaMYB28 was 1257 bp with an ORF of 1020 bp. The deduced BoaMYB28 protein was a polypeptide of 339 amino acid with a putative molecular mass of 38 kDa and a pI of 6.87. Sequence homology and phylogenetic analysis showed that BoaMYB28 was most closely related to MYB28 homologs from the Brassicaceae family. The expression levels of BoaMYB28 varies across the tissues and developmental stages. BoaMYB28 transcript levels were higher in leaves and stems compared with those in cotyledons, flowers, and siliques. BoaMYB28 was expressed across all developmental leaf stages, with higher transcript accumulation in mature and inflorescence leaves. Over-expression and RNAi studies showed that BoaMYB28 retains the basic MYB28 gene function as a major transcriptional regulator of aliphatic glucosinolate pathway. The results indicated that over-expression and RNAi lines showed no visible difference on plant morphology. The contents of aliphatic glucosinolates and transcript levels of aliphatic glucosinolate biosynthesis genes increased in over-expression lines and decreased in RNAi lines. In over-expression lines, aliphatic glucosinolate contents were 1.5- to 3-fold higher than those in the wild-type, while expression levels of aliphatic glucosinolate biosynthesis genes were 1.5- to 4-fold higher than those in the wild-type. In contrast, the contents of aliphatic glucosinolates and transcript levels of aliphatic glucosinolate

Molecular Characterization of MYB28 Involved in Aliphatic Glucosinolate Biosynthesis in Chinese Kale (Brassica oleracea var. alboglabra Bailey).

Science.gov (United States)

Yin, Ling; Chen, Hancai; Cao, Bihao; Lei, Jianjun; Chen, Guoju

2017-01-01

Glucosinolates are Brassicaceae-specific secondary metabolites that act as crop protectants, flavor precursors, and cancer-prevention agents, which shows strong evidences of anticarcinogentic, antioxidant, and antimicrobial activities. MYB28 , the R2R3-MYB28 transcription factor, directly activates genes involved in aliphatic glucosinolate biosynthesis. In this study, the MYB28 homology ( BoaMYB28 ) was identified in Chinese kale ( Brassica oleracea var. alboglabra Bailey). Analysis of the nucleotide sequence indicated that the cDNA of BoaMYB28 was 1257 bp with an ORF of 1020 bp. The deduced BoaMYB28 protein was a polypeptide of 339 amino acid with a putative molecular mass of 38 kDa and a pI of 6.87. Sequence homology and phylogenetic analysis showed that BoaMYB28 was most closely related to MYB28 homologs from the Brassicaceae family. The expression levels of BoaMYB28 varies across the tissues and developmental stages. BoaMYB28 transcript levels were higher in leaves and stems compared with those in cotyledons, flowers, and siliques. BoaMYB28 was expressed across all developmental leaf stages, with higher transcript accumulation in mature and inflorescence leaves. Over-expression and RNAi studies showed that BoaMYB28 retains the basic MYB28 gene function as a major transcriptional regulator of aliphatic glucosinolate pathway. The results indicated that over-expression and RNAi lines showed no visible difference on plant morphology. The contents of aliphatic glucosinolates and transcript levels of aliphatic glucosinolate biosynthesis genes increased in over-expression lines and decreased in RNAi lines. In over-expression lines, aliphatic glucosinolate contents were 1.5- to 3-fold higher than those in the wild-type, while expression levels of aliphatic glucosinolate biosynthesis genes were 1.5- to 4-fold higher than those in the wild-type. In contrast, the contents of aliphatic glucosinolates and transcript levels of aliphatic glucosinolate biosynthesis genes in

Aliphatic alcohols of illegally produced spirits can act synergistically on superoxide-anion production by human granulocytes.

Science.gov (United States)

Arnyas, Ervin M; Pál, László; Kovács, Csilla; Adány, Róza; McKee, Martin; Szűcs, Sándor

2012-10-01

Aliphatic alcohols present in illegally produced spirits in a large number of low and middle income countries have been implicated in the etiology of chronic liver disease and cirrhosis. Previous studies have confirmed that chronic alcoholism can lead to increased susceptibility to infectious diseases. Reduced superoxide-anion (O(2)·(-)) production by granulocytes could provide a mechanism by which antimicrobial defense is impaired in alcoholics. In vitro experiments have also demonstrated that ethanol can inhibit granulocyte O(2)·(-) generation. Aliphatic alcohols consumed as contaminants of illicit spirits may also influence O(2)·(-) production thereby contributing to a decrease in microbicidal activity. The aim of this study was to investigate this possibility. It measured the O(2)·(-) production by human granulocytes following treatment of the cells with aliphatic alcohol contaminants found in illicit spirits. Granulocytes were isolated from human buffy coats with centrifugal elutriation and then treated with individual aliphatic alcohols and their mixture. The O(2)·(-) production was stimulated with phorbol-12-13-dibutyrate and N-formyl-methionyl-leucyl-phenylalanine (FMLP) and measured by superoxide dismutase inhibitable reduction of ferricytochrome c. Aliphatic alcohols of illegally produced spirits inhibited the FMLP-induced O(2)·(-) production in a concentration dependent manner. They suppressed O(2)·(-) generation at 2.5-40 times lower concentrations when combined than when tested individually. Aliphatic alcohols found in illegally produced spirits can inhibit FMLP-induced O(2)·(-) production by granulocytes in a concentration-dependent manner. Due to their synergistic effects, it is possible that, in combination with ethanol, they may inhibit O(2)·(-) formation in heavy episodic drinkers.

Palladium-catalyzed aryl C-H olefination with unactivated, aliphatic alkenes.

Science.gov (United States)

Deb, Arghya; Bag, Sukdev; Kancherla, Rajesh; Maiti, Debabrata

2014-10-01

Palladium-catalyzed coupling between aryl halides and alkenes (Mizoroki-Heck reaction) is one of the most popular reactions for synthesizing complex organic molecules. The limited availability, problematic synthesis, and higher cost of aryl halide precursors (or their equivalents) have encouraged exploration of direct olefination of aryl carbon-hydrogen (C-H) bonds (Fujiwara-Moritani reaction). Despite significant progress, the restricted substrate scope, in particular noncompliance of unactivated aliphatic olefins, has discouraged the use of this greener alternative. Overcoming this serious limitation, we report here a palladium-catalyzed chelation-assisted ortho C-H bond olefination of phenylacetic acid derivatives with unactivated, aliphatic alkenes in good to excellent yields with high regio- and stereoselectivities. The versatility of this operationally simple method has been demonstrated through drug diversification and sequential C-H olefination for synthesizing divinylbenzene derivatives.

Occurrence and Sources of Aliphatic Hydrocarbons in Soils within ...

African Journals Online (AJOL)

ADOWIE PERE

Keywords: Asphalt Plants; Soil; Aliphatic hydrocarbons; Pristane; Phytane. Hot mix asphalt (HMA) plant is an assemblage of mechanical equipment where aggregates or inert mineral materials such as sand, gravel, crushed stones, Slag, rock dust or powder are blended, heated, dried and mixed with bitumen in measured ...

The Feasibility of Enzyme Targeted Activation for Amino Acid/Dipeptide Monoester Prodrugs of Floxuridine; Cathepsin D as a Potential Targeted Enzyme

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Gordon L. Amidon

2012-03-01

Full Text Available The improvement of therapeutic efficacy for cancer agents has been a big challenge which includes the increase of tumor selectivity and the reduction of adverse effects at non-tumor sites. In order to achieve those goals, prodrug approaches have been extensively investigated. In this report, the potential activation enzymes for 5¢-amino acid/dipeptide monoester floxuridine prodrugs in pancreatic cancer cells were selected and the feasibility of enzyme specific activation of prodrugs was evaluated. All prodrugs exhibited the range of 3.0–105.7 min of half life in Capan-2 cell homogenate with the presence and the absence of selective enzyme inhibitors. 5¢-O-L-Phenylalanyl-L-tyrosyl-floxuridine exhibited longer half life only with the presence of pepstatin A. Human cathepsin B and D selectively hydrolized 5¢-O-L-phenylalanyl-L-tyrosylfloxuridine and 5¢-O-L-phenylalanyl-L-glycylfloxuridine compared to the other tested prodrugs. The wide range of growth inhibitory effect by floxuridine prodrugs in Capan-2 cells was observed due to the different affinities of prodrug promoieties to enyzmes. In conclusion, it is feasible to design prodrugs which are activated by specific enzymes. Cathepsin D might be a good candidate as a target enzyme for prodrug activation and 5¢-O-L-phenylalanyl-L-tyrosylfloxuridine may be the best candidate among the tested floxuridine prodrugs.

The feasibility of enzyme targeted activation for amino acid/dipeptide monoester prodrugs of floxuridine; cathepsin D as a potential targeted enzyme.

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Tsume, Yasuhiro; Amidon, Gordon L

2012-03-26

The improvement of therapeutic efficacy for cancer agents has been a big challenge which includes the increase of tumor selectivity and the reduction of adverse effects at non-tumor sites. In order to achieve those goals, prodrug approaches have been extensively investigated. In this report, the potential activation enzymes for 5'-amino acid/dipeptide monoester floxuridine prodrugs in pancreatic cancer cells were selected and the feasibility of enzyme specific activation of prodrugs was evaluated. All prodrugs exhibited the range of 3.0-105.7 min of half life in Capan-2 cell homogenate with the presence and the absence of selective enzyme inhibitors. 5'-O-L-Phenylalanyl-L-tyrosyl-floxuridine exhibited longer half life only with the presence of pepstatin A. Human cathepsin B and D selectively hydrolized 5'-O-L-phenylalanyl-L-tyrosylfloxuridine and 5'-O-L-phenylalanyl-L-glycylfloxuridine compared to the other tested prodrugs. The wide range of growth inhibitory effect by floxuridine prodrugs in Capan-2 cells was observed due to the different affinities of prodrug promoieties to enzymes. In conclusion, it is feasible to design prodrugs which are activated by specific enzymes. Cathepsin D might be a good candidate as a target enzyme for prodrug activation and 5'-O-L-phenylalanyl-L-tyrosylfloxuridine may be the best candidate among the tested floxuridine prodrugs.

40 CFR 721.6140 - Dialkyldithiophosphoric acid, aliphatic amine salt.

Science.gov (United States)

2010-07-01

... methods for protecting against such risk, into an MSDS as described in § 721.72(c) within 90 days from the..., aliphatic amine salt. 721.6140 Section 721.6140 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... manner or method of manufacture, import, or processing associated with any use of this substance without...

Direct electrochemical imidation of aliphatic amines via anodic oxidation.

Science.gov (United States)

Zhang, Li; Su, Ji-Hu; Wang, Sujing; Wan, Changfeng; Zha, Zhenggen; Du, Jiangfeng; Wang, Zhiyong

2011-05-21

Direct electrochemical synthesis of sulfonyl amidines from aliphatic amines and sulfonyl azides was realized with good to excellent yields. Traditional tertiary amine substrates were broadened to secondary and primary amines. The reaction intermediates were observed and a reaction mechanism was proposed and discussed. © The Royal Society of Chemistry 2011

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

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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.

Kinetics of Oxidation of Aliphatic Alcohols by Potassium Dichromate ...

African Journals Online (AJOL)

The kinetics of oxidation of four aliphatic alcohols in acidic aqueous and micellar media were investigated. The reaction was found to be first-order with respect to both alcohol and oxidant. Pseudo-first-order kinetics were found to be perfectly applicable with ethanol, 1-propanol and 2-propanol while deviation was observed ...

Modification of Aliphatic Petroleum Resin by Peracetic Acid

OpenAIRE

Bondaletov, Vladimir Grigoryevich; Bondaletova, Lyudmila Ivanovna; Hamlenko, A.; Bondaletov, Oleg Vladimirovich; Starovoit, M.

2014-01-01

This work demonstrates the possibility of obtaining modified aliphatic resin (PRC5) by means of petroleum resin oxidation by peracetic acid. We have experimentally determined oxidation conditions that lead to producing resin with maximum epoxy and acid numbers. Ratio of "oxidative system: PRC5" is 0.5:1, process duration is 2 hours. The modified resin structure is determined by IR and NMR spectroscopy.

Kinetics and mechanism of oxidation of aliphatic primary alcohols by ...

Indian Academy of Sciences (India)

Unknown

Kinetics and mechanism of oxidation of aliphatic primary alcohols by quinolinium bromochromate. SONU SARASWAT, VINITA SHARMA and K K BANERJI*. Department of Chemistry, JNV University, Jodhpur 342 005, India e-mail: banerjikk@rediffmail.com. MS received 4 December 2001; revised 2 November 2002.

Hydrodeoxygenation of aliphatic and aromatic oxygenates on sulphided catalysts for production of second generation biofuels

Energy Technology Data Exchange (ETDEWEB)

Senol, O.I.

2007-07-01

Environmental concerns and diminishing petroleum reserves have increased the importance of biofuels for traffic fuel applications. Second generation biofuels produced from wood, vegetable oils and animal fats have been considered promising for delivering biofuels in large amount with low production cost. The abundance of oxygen in the form of various aliphatic and aromatic oxygenates decreases the quality of biofuels, however, and therefore the oxygen content of biofuels must be reduced. Upgrading of biofuels can be achieved by hydrodeoxygenation (HDO), which is similar to hydrodesulphurisation in oil refining. In HDO, oxygen-containing compounds are converted to hydrocarbons by eliminating oxygen in the form of water in the presence of hydrogen and a sulphided catalyst. Due to the low sulphur content of biofuels, a sulphiding agent is typically added to the HDO feed to maintain activity and stability of the catalyst. The aim of this work was to investigate HDO using aliphatic and aromatic oxygenates as model compounds on sulphided NiMo/gamma-Al{sub 2}O3 and CoMo/gamma-Al{sub 2}O3 catalysts. The effects of side product, water, and of sulphiding agents, H{sub 2}S and CS{sub 2}, on HDO were determined. The primary focus was on the HDO of aliphatic oxygenates, because a reasonable amount of data regarding the HDO of aromatic oxygenates already exists. The HDO of aliphatic esters produced hydrocarbons from intermediate alcohol, carboxylic acid, aldehyde and ether compounds. A few sulphur-containing compounds were also detected in trace amounts, and their formation caused desulphurisation of the catalysts. Hydrogenation reactions and acid-catalysed reactions (dehydration, hydrolysis, esterification, E{sub 2} elimination and SN{sub 2} nucleophilic substitution) played a major role in the HDO of aliphatic oxygenates. The NiMo catalyst showed a higher activity for HDO and hydrogenation reactions than the CoMo catalyst, but both catalysts became deactivated because of

Sum frequency generation image reconstruction: Aliphatic membrane under spherical cap geometry

Energy Technology Data Exchange (ETDEWEB)

Volkov, Victor [Bereozovaya 2A, Konstantinovo, Moscow Region 140207 (Russian Federation)

2014-10-07

The article explores an opportunity to approach structural properties of phospholipid membranes using Sum Frequency Generation microscopy. To establish the principles of sum frequency generation image reconstruction in such systems, at first approach, we may adopt an idealistic spherical cap uniform assembly of hydrocarbon molecules. Quantum mechanical studies for decanoic acid (used here as a representative molecular system) provide necessary information on transition dipole moments and Raman tensors of the normal modes specific to methyl terminal – a typical moiety in aliphatic (and phospholipid) membranes. Relative degree of localization and frequencies of the normal modes of methyl terminals make nonlinearities of this moiety to be promising in structural analysis using Sum Frequency Generation imaging. Accordingly, the article describes derivations of relevant macroscopic nonlinearities and suggests a mapping procedure to translate amplitudes of the nonlinearities onto microscopy image plane according to geometry of spherical assembly, local molecular orientation, and optical geometry. Reconstructed images indicate a possibility to extract local curvature of bilayer envelopes of spherical character. This may have practical implications for structural extractions in membrane systems of practical relevance.

Aliphatic-aromatic separation using deep eutectic solvents as extracting agents

NARCIS (Netherlands)

Rodriguez Rodriguez, Nerea; Fernandez Requejo, Patricia; Kroon, Maaike

2015-01-01

The separation of aliphatic and aromatic compounds is a great challenge for chemical engineers. There is no efficient separation process for mixtures with compositions lower than 20 wt % in aromatics. In this work, the feasibility of two different deep eutectic solvents (DESs) as novel extracting

An enzyme-linked immunosorbent assay for monoester-type aconitic alkaloids and its application in the pharmacokinetic study of benzoylhypaconine in rats.

Science.gov (United States)

Liu, Can-Can; Xu, Yun-Hui; Yuan, Shuai; Xu, Yu; Hua, Mo-Li

2018-04-01

A new enzyme-linked immunosorbent assay (ELISA) method for quantitative determination of monoester-type aconitic alkaloids was developed. The antibodies derived from the immunogen of benzoylmesaconine (BM) could be electively affined to benzoylaconitine-type alkaloids with an ester bond (14-benzoyl-), especially to benzoylhypaconine (BH, 140.02% of cross-reactivity). The effective working range of BH was 1 ng/ml to 5 μg/ml; the lower limit of detection and the quantification were 0.35 and 0.97 ng/ml, respectively. The values of CV for intra-day and inter-day assays and recovery ratios were in acceptable ranges. The results of stability experiments were also satisfactory. This validated method was employed for pharmacokinetic study of BH in rats and the bioavailability orally administered was estimated to be 16.3%.

The effect of mechanical loads on the degradation of aliphatic biodegradable polyesters.

Science.gov (United States)

Li, Ying; Chu, Zhaowei; Li, Xiaoming; Ding, Xili; Guo, Meng; Zhao, Haoran; Yao, Jie; Wang, Lizhen; Cai, Qiang; Fan, Yubo

2017-06-01

Aliphatic biodegradable polyesters have been the most widely used synthetic polymers for developing biodegradable devices as alternatives for the currently used permanent medical devices. The performances during biodegradation process play crucial roles for final realization of their functions. Because physiological and biochemical environment in vivo significantly affects biodegradation process, large numbers of studies on effects of mechanical loads on the degradation of aliphatic biodegradable polyesters have been launched during last decades. In this review article, we discussed the mechanism of biodegradation and several different mechanical loads that have been reported to affect the biodegradation process. Other physiological and biochemical factors related to mechanical loads were also discussed. The mechanical load could change the conformational strain energy and morphology to weaken the stability of the polymer. Besides, the load and pattern could accelerate the loss of intrinsic mechanical properties of polymers. This indicated that investigations into effects of mechanical loads on the degradation should be indispensable. More combination condition of mechanical loads and multiple factors should be considered in order to keep the degradation rate controllable and evaluate the degradation process in vivo accurately. Only then can the degradable devise achieve the desired effects and further expand the special applications of aliphatic biodegradable polyesters.

In vitro evaluation of aliphatic fatty alcohol metabolites of ...

African Journals Online (AJOL)

From the seeds of P. americana, five known 1, 2, 4-dihydroxy derivatives aliphatic alcohols, called avocadenols were isolated and identified by spectroscopic methodsincluding 1D- and 2D NMR, and comparison with reported data in literature. Antifungal activity for 1, 2, 4-Trihydroxyheptadec-6-en-16-yne (5)(IC50< 8 μg/mL) ...

Vapor Pressure of Selected Aliphatic Alcohols by Ebulliometry. Part 1

Czech Academy of Sciences Publication Activity Database

Čenský, M.; Roháč, V.; Růžička, K.; Fulem, M.; Aim, Karel

2010-01-01

Roč. 298, č. 2 (2010), s. 192-198 ISSN 0378-3812 R&D Projects: GA AV ČR IAA400720710 Institutional research plan: CEZ:AV0Z40720504 Keywords : vapor pressure * ebulliometry * aliphatic alcohols Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.253, year: 2010

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

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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.

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

Directory of Open Access Journals (Sweden)

Valerie Vranova

2013-01-01

Full Text Available 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.

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

Science.gov (United States)

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

Chlorinated aliphatic and aromatic VOC decomposition in air mixture by using electron beam irradiation

International Nuclear Information System (INIS)

Chmielewski, A.G.; Sun Yongxia; Bulka, S.; Zimek, Z.

2004-01-01

Chlorinated aliphatic and aromatic hydrocarbons, which are emitted from coal power station and waste incinerators, are very harmful to the environment and human health. Recent studies show that chlorinated aliphatic and aromatic hydrocarbons are suspected to be the precursors of dioxin's formation. Dioxin's emission into atmosphere will cause severe environmental problems by ecology contamination. l,4-dichlorobenzene(l,4-DCB) and cis-dichloroethylene(cis-DCE) were chosen as representative chlorinated aromatic and aliphatic compounds, respectively. Their decomposition was investigated by electron beam irradiation. The experiments were carried out 'in batch' system. It is found that over 97% cis-DCE is decomposed having an initial concentration of 661 ppm. G-values of cis-DCE decomposition vary from 10 to 28 (molecules/100 eV) for initial concentration of 270-1530 ppm cis-DCE. The decomposition is mainly caused by secondary electron attachment and Cl addition reactions. Comparing with cis-DCE, 1,4-DCB decomposition needs higher absorbed dose. G-value of 1,4-DCB is below 4 molecules/100 eV

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

Science.gov (United States)

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Kinetic isotope effects and aliphatic diazo-compounds

International Nuclear Information System (INIS)

Albery, W.J.; Conway, C.W.; Hall, J.A.

1976-01-01

Results are reported for the variation of the rate of decomposition of ethyl diazomalonate (EDM) and diazomalonate anions with pH and for the deuterium solvent isotope effect for EDM. The shape of the pH profile is explained by successive protonations of the anions. Ethyl diazoacetate is observed as an intermediate in the decomposition of EDM. The degree of proton transfer in the EDM transition state is deduced from the solvent isotope effect and the results together with those for other aliphatic diazo-compounds are discussed in terms of the Marcus theory. (author)

Distribution of aliphatic and polycyclic aromatic hydrocarbon in South China sea sediments

International Nuclear Information System (INIS)

Md Suhaimi Elias; Ab Khalik Wood; Zaleha Hashim; Wee Boon Siong; Nazaratul Ashifa; Mohd Suhaimi Hamzah; Shamsiah Ab Rahman; Ariffin Talib

2006-01-01

Petroleum hydrocarbon (Hcp) consist of three major components namely alkanes, cyclo-alkanes and aromatics. HCP are pollutant and can cause adverse effect to the marine organisms. The study was done to identify the source of pollution in the South China Sea coastal area. The South China Sea is one of the major oil production area in Malaysia. Sampling was done at 15 stations along the coastal area of South China Sea off Peninsular Malaysia, which involved two zone namely coastal (zone 1) and offshore (zone 2) areas. Samples were analyzed using GC-MS for determination of HCP. The results showed, that concentration of aliphatic and polycyclic aromatic hydrocarbon at coastal area, range from 0.51 - 1.31 mg/g and 0.18 - 0.42 mg/g dry weight, respectively whilst, concentration of aliphatic and polycyclic aromatic hydrocarbon at offshore area, range from 0.44 - 1.09 mg/g and 0.20 - 0.49 mg/g dry weight, respectively. SHCP (Aliphatic + PAH) concentration in the sediment at the study area range from 0.64 - 1.68 mg/g dry weight. In this study, it was found that, pollution source for the South China Sea off Peninsular Malaysia was originated from pyrolytic sources (combustion fossil fuel), while some other area had been polluted by pyrolytic or petrogenic (unburned fossil) sources. (Author)

Cyclohexane/benzene organic glasses and ethylene/styrene copolymers behaviour under ionizing radiations: energy and species transfers between aliphatic and aromatic moieties

International Nuclear Information System (INIS)

Ferry, M.

2008-11-01

The aim of this study is to understand how aliphatic and aromatic groups interact under ionizing radiations. Three research orientations were explored: the determination of the relative contribution of energy and radical transfers, the determination of the intermolecular and intra-chain relative contribution, and the influence of the repartition of the aliphatic and aromatic units inside the polymer chain. Three systems composed of aromatic and aliphatic units were studied: the cyclohexane/benzene organic glasses (intermolecular reactions), the ethylene/styrene random copolymers (inter-chain and intra-chain reactions) and ethylene/styrene di-blocs copolymers (influence of the repartition of the aliphatic and aromatic units in the material). Considering the results obtained, we have concluded that energy transfers are important in the radiation protection effect of the aliphatic moiety by the aromatic one, although radical transfers are also contributing. Intermolecular transfers are efficient in the solid state and their efficiency seems equivalent to that of the intra-chain ones. Thanks to the use of infrared spectroscopy, we have shown an important effect of radiation sensitization of the aromatic moiety, whatever the irradiation temperature and the system studied: energy transfers to the aromatic moiety are carried out at the detriment of its stability. Finally, the repartition of the aliphatic and aromatic units in the polymer chain is not an important factor in the effects induced by the energy transfers. (author)

Oxyfunctionalization of the Remote C-H Bonds of Aliphatic Amines by Decatungstate Photocatalysis.

Science.gov (United States)

Schultz, Danielle M; Lévesque, François; DiRocco, Daniel A; Reibarkh, Mikhail; Ji, Yining; Joyce, Leo A; Dropinski, James F; Sheng, Huaming; Sherry, Benjamin D; Davies, Ian W

2017-11-27

Aliphatic amines, oxygenated at remote positions within the molecule, represent an important class of synthetic building blocks to which there are currently no direct means of access. Reported herein is an efficient and scalable solution that relies upon decatungstate photocatalysis under acidic conditions using either H 2 O 2 or O 2 as the terminal oxidant. By using these reaction conditions a series of simple and unbiased aliphatic amine starting materials can be oxidized to value-added ketone products. Lastly, NMR spectroscopy using in situ LED-irradiated samples was utilized to monitor the kinetics of the reaction, thus enabling direct translation of the reaction into flow. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Swift Heavy Ion Induced Modification of Aliphatic Polymers

OpenAIRE

Hossain, Umme Habiba

2015-01-01

In this thesis, the high energy heavy ion induced modification of aliphatic polymers is studied. Two polymer groups, namely polyvinyl polymers (PVF, PVAc, PVA and PMMA) and fluoropolymers (PVDF, ETFE, PFA and FEP) were used in this work. Polyvinyl polymers were investigated since they will be used as insulating materials in the superconducting magnets of the new ion accelerators of the planned International Facility for Antiproton and Ion Research (FAIR) at the GSI Helmholtz-Centre of Heavy I...

Kinetics of aerobic cometabolic biodegradation of chlorinated and brominated aliphatic hydrocarbons: A review.

Science.gov (United States)

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. Copyright © 2016 Elsevier B.V. All rights reserved.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products. [Polychlorinated biphenyls; methylene chloride; perchloroethylene; trichlorofluoroethane; trichloroethylene; chlorobenzene

Science.gov (United States)

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.

Characterization, Distribution, Sources and Origins of Aliphatic Hydrocarbons from Surface Sediment of Prai Strait, Penang, Malaysia: A Widespread Anthropogenic Input

Directory of Open Access Journals (Sweden)

Mahyar Sakari

2008-07-01

Full Text Available Persistent organic pollutants such as petroleum hydrocarbons are one of the most serious and important class of pollutants that face to many countries including Malaysia. Aliphatic hydrocarbons contain straight chain alkane; derive from anthropogenic and natural sources to the marine environment. The multi-purpose strait of Prai is located in the Northwest of Peninsular Malaysia plays an important economic role in the Southeast Asia. Twenty surface sediment samples were collected using Eckman dredge to measure the concentration and determine the characterization, sources and origins of the aliphatic hydrocarbons in December 2006. Samples (top 4 cm were extracted with Soxhlet, treated with activated copper and subjected to 2 steps column chromatography for purification and fractionation. Alkane fraction injected into Gas Chromatography–Flame Ionization Detector (GC-FID for instrumental analysis. The results showed that total n-alkane concentrations are ranging from 512 to 10770 ng/mg d. w. Carbon Preferences Index (CPI revealed an extreme widespread anthropogenic input and naturally derived (CPI= 0 to 4.88 hydrocarbons in the study area. The ratio of C31/C19 indicated that natural hydrocarbons are generating from terrestrial vascular plants and transferring by rivers. The characteristics of Major Hydrocarbons provided evidences that oil and its derivatives either fresh or degraded are the major contributors of the pollution in the study area. Statistical approaches also confirmed that 85% of study area affected by oil sources of pollution. It is seen that aliphatic hydrocarbons mostly transfer by lateral input to the marine environment than atmospheric movements.

Corrosion inhibition of brass by aliphatic amines

International Nuclear Information System (INIS)

Taha, K. K.; Sheshadri, B. S; Ahmed, M. F.

2005-01-01

Aliphatic amines hexylamine (HCA), octylamine (OCA) and decylamine (DCA) have been used as corrosion inhibitors for (70/30) brass in 0.I M HCIO 4 . The inhibitor efficiency (%P) calculated using weight loss, Tafel extrapolation, linear polarization and impedance methods was found to be in the order DCA> OCA> HCA. These adsorb on brass surface following bockris-swinkels' isotherm. DCA, OCA and HCA displaced 4, 3 and 2 molecules of water from interface respectively. Displacement of water molecules brought a great reorganization of double layer at the interface. These amines during corrosion form complexes with dissolved zinc and copper ions.(Author)

Organic pollutants in the coastal environment off San Diego, California. 2: Petrogenic and biogenic sources of aliphatic hydrocarbons

International Nuclear Information System (INIS)

Tran, K.; Yu, C.C.; Zeng, E.Y.

1997-01-01

The results from the measurements of aliphatic hydrocarbons suggest that hydrocarbons suggest that hydrocarbons in the Point Loma Wastewater Treatment Plant (PLWTP) effluents are mainly petroleum derived; those in the Tijuana River runoff have largely originated from terrestrial plants with visible petroleum contamination; and those in the sea surface microlayer, sediment traps, and sediments at various coastal locations off San Diego have mostly resulted from biogenic contributions with enhanced microbial products in the summer season. Rainfall in the winter season appeared to amplify the inputs from terrestrial higher plants to the coastal areas. The PLWTP discharged approximately 3.85 metric tons of n-alkanes (C 10 -C 35 ) in 1994, well below the level (136 metric tons) estimated in 1979. The input of aliphatic hydrocarbons from the Tijuana River was about 0.101 metric tons in 1994. Diffusion, solubilization, evaporation, and microbial degradation seemed partially responsible for the difference in the concentrations and compositions of aliphatic hydrocarbons in different sample media, although the relative importance of each mechanism cannot be readily discerned from the available data. The results from analyses of aliphatic hydrocarbon compositional indices are generally consistent with those of polycyclic aromatic hydrocarbons

Colorless triphenylamine-based aliphatic thermoset epoxy for multicolored and near-infrared electrochromic applications.

Science.gov (United States)

Chuang, Ya-Wen; Yen, Hung-Ju; Wu, Jia-Hao; Liou, Guey-Sheng

2014-03-12

In this study, two novel colorless thermoset epoxy resins with anodically electrochromism were prepared from the thermal curing of two triphenylamine-based diamine monomers, 4,4'-diamino-4″-methoxytriphenylamine (1) and N,N'-bis(4-aminophenyl)-N,N'-di(4-methoxylphenyl)-1,4-phenylenediamine (2) with aliphatic epoxy triglycidyl isocyanurate, respectively. The resulting thermoset epoxy resins showed excellent softening temperature (Ts, 270 and 280 °C) due to the rigid structure and highly crosslinking density. In addition, novel colorless epoxy resin films revealed good reversible electrochemical oxidation and interesting multi-electrochromic behavior with high contrast ratio both in visible and near-infrared regions. The aliphatic thermoset epoxy resins also exhibited high transparency in visible region as colorless and great potential for practical electrochromic applications.

Effect of electron beam irradiation on the biodegradability of aromatic aliphatic copolyester film and their blend with corn starch

International Nuclear Information System (INIS)

Silva, Leonardo G. Andrade e; Poveda, Patricia N.S.; Rezende, Maira L.; Rosa, Derval S.

2009-01-01

Biodegradable and green plastics have been studied in the last years. The aim of this paper is to study the effect of electron beam irradiation on the biodegradability of aromatic aliphatic copolyester film and their blend with corn starch. The samples were irradiated at different doses 10 and 40 kGy in a linear accelerator. The biodegradability of the materials was evaluated by two methods: soil simulated and enzymatic. In the method enzymatic when it was used α-amylase, the irradiated samples presented faster biodegradation than the references non irradiated. The blend of aromatic aliphatic copolyester with corn starch (Ecobras R ) irradiated presented a bigger biodegradability than the aromatic aliphatic copolyester (Ecoflex R ) film in both methods studied. (author)

Gamma radiolysis of aliphatic sulfur compounds in aqueous solutions. A study to contribute to the analysis of the end products of the OH radical-induced oxidation of aliphatic mercaptanes, sulfides, and disulfides

International Nuclear Information System (INIS)

Weiss, J.

1982-01-01

By identifying and determining numerous hitherto unknown end products, the study in hand contributes to a better insight into the radiation chemical processes occurring in OH radical-induced oxidation of aliphatic sulfur compounds. An extraction method has been developed for the qualitative and quantitative analysis of end products in aqueous solution in order to determine these compounds down to the level of trace amounts. Separation of endproducts is achieved by means of gas chromatography and high-pressure liquid chromatography, subsequent identification by GC-MS analysis. Aliphatic mercaptanes are oxidized by OH radicals to thiyl radicals which after combination can be detected as disulfide. At high radiation doses, secondary reactions will lead to polysulfides of which the homologues could first be prepared as the pure substance. The end products of the γ-radiolysis of aliphatic thioethers are determined to be dithia compounds, symmetrical or asymmetrical disulfides, or polysulfides, depending on the thioethers. With some end products, the radiation chemical yield is found to be a function of the absorbed dose so that material balances are impossible. Intermediate thiyl, α-alkyl mercaptoalkyl or alkyl radicals can be captured by tetramethyl ethylene, cyclohexene or p-benzoquinone, and can then be identified as the relevant adducts. (orig./RB) [de

Aliphatic acetogenin constituents of avocado fruits inhibit human oral cancer cell proliferation by targeting the EGFR/RAS/RAF/MEK/ERK1/2 pathway

Energy Technology Data Exchange (ETDEWEB)

D' Ambrosio, Steven M. [Department of Radiology, College of Medicine, The Ohio State University, Columbus, OH 43210 (United States); Comprehensive Cancer Center, The Ohio State University, Columbus, OH 43210 (United States); Han, Chunhua [Department of Radiology, College of Medicine, The Ohio State University, Columbus, OH 43210 (United States); Pan, Li; Douglas Kinghorn, A. [Division of Medicinal Chemistry and Pharmacognosy, College of Pharmacy, The Ohio State University, Columbus, OH 43210 (United States); Ding, Haiming, E-mail: ding.29@osu.edu [Department of Radiology, College of Medicine, The Ohio State University, Columbus, OH 43210 (United States)

2011-06-10

Highlights: {yields} The aliphatic acetogenins [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] (1) and [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate] (2) isolated from avocado fruit inhibit phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). {yields} Aliphatic acetogenin 2, but not 1, prevents EGF-induced activation of EGFR (Tyr1173). {yields} Combination of both aliphatic acetogenins synergistically inhibits c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204) phosphorylation and human oral cancer cell proliferation. {yields} The potential anticancer activity of avocado fruits is due to a combination of specific aliphatic acetogenins targeting two key components of the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. {yields} Providing a double hit on a critical cancer pathway such as EGFR/RAS/RAF/MEK/ERK1/2 by phytochemicals like those found in avocado fruit could lead to more effective approach toward cancer prevention. -- Abstract: Avocado (Persea americana) fruits are consumed as part of the human diet and extracts have shown growth inhibitory effects in various types of human cancer cells, although the effectiveness of individual components and their underlying mechanism are poorly understood. Using activity-guided fractionation of the flesh of avocado fruits, a chloroform-soluble extract (D003) was identified that exhibited high efficacy towards premalignant and malignant human oral cancer cell lines. From this extract, two aliphatic acetogenins of previously known structure were isolated, compounds 1 [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] and 2 [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate]. In this study, we show for the first time that the growth inhibitory efficacy of this chloroform extract is due to blocking the phosphorylation of EGFR (Tyr1173), c-RAF (Ser338), and ERK1/2 (Thr202/Tyr204) in the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. Compounds 1 and 2 both inhibited phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). Compound 2, but not

Aliphatic acetogenin constituents of avocado fruits inhibit human oral cancer cell proliferation by targeting the EGFR/RAS/RAF/MEK/ERK1/2 pathway

International Nuclear Information System (INIS)

D'Ambrosio, Steven M.; Han, Chunhua; Pan, Li; Douglas Kinghorn, A.; Ding, Haiming

2011-01-01

Highlights: → The aliphatic acetogenins [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] (1) and [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate] (2) isolated from avocado fruit inhibit phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). → Aliphatic acetogenin 2, but not 1, prevents EGF-induced activation of EGFR (Tyr1173). → Combination of both aliphatic acetogenins synergistically inhibits c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204) phosphorylation and human oral cancer cell proliferation. → The potential anticancer activity of avocado fruits is due to a combination of specific aliphatic acetogenins targeting two key components of the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. → Providing a double hit on a critical cancer pathway such as EGFR/RAS/RAF/MEK/ERK1/2 by phytochemicals like those found in avocado fruit could lead to more effective approach toward cancer prevention. -- Abstract: Avocado (Persea americana) fruits are consumed as part of the human diet and extracts have shown growth inhibitory effects in various types of human cancer cells, although the effectiveness of individual components and their underlying mechanism are poorly understood. Using activity-guided fractionation of the flesh of avocado fruits, a chloroform-soluble extract (D003) was identified that exhibited high efficacy towards premalignant and malignant human oral cancer cell lines. From this extract, two aliphatic acetogenins of previously known structure were isolated, compounds 1 [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] and 2 [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate]. In this study, we show for the first time that the growth inhibitory efficacy of this chloroform extract is due to blocking the phosphorylation of EGFR (Tyr1173), c-RAF (Ser338), and ERK1/2 (Thr202/Tyr204) in the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. Compounds 1 and 2 both inhibited phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). Compound 2, but not compound 1, prevented EGF

Aliphatic Nucleophilic Radio-fluorination

International Nuclear Information System (INIS)

Roeda, D.; Dolle, F.

2010-01-01

In this review we are looking at some aspects of nucleophilic aliphatic radio-fluorination, notably the labelled fluoride source, design aspects, the leaving group and the solvent. It should be clear that there is more to this branch of radiolabelling than one would suspect from the frequently used standard tosylate replacement with kryptofix/[ 18 F]fluoride in acetonitrile or DMSO. Competitive elimination can be a serious problem that can affect both yield and purification. De-protection of sensitive groups after radiolabelling and its possible side reactions can complicate purification. The right choice of leaving group and protecting groups may be crucial. Newer developments such as the use of tertiary alcohols or ionic liquids as solvents, long-chain poly-fluorinated sulphonate leaving groups facilitating fluorous solid phase extraction, or immobilisation of the precursor on a solid phase support may help to solve these problems, for example the longstanding problems with [ 18 F]FLT, whereas older concepts such as certain cyclic reactive entities for ring opening or even an abandoned reagent as [ 18 F]DAST should not be forgotten. (authors)

Development and application of bacterial cultures for the removal of chlorinated aliphatics

NARCIS (Netherlands)

Janssen, Dick B.; de Koning, Wim

1995-01-01

The possibility of obtaining microbial cultures for the degradation of halogenated aliphatic hydrocarbons is mainly determined by the diversity and activity of catabolic enzymes that exist in nature. If a suitable organism is available, applications for the treatment of different waste streams can

Critical properties of some aliphatic symmetrical ethers

International Nuclear Information System (INIS)

Nikitin, Eugene D.; Popov, Alexander P.; Bogatishcheva, Nataliya S.

2014-01-01

Highlights: • Critical properties of simple aliphatic ethers were measured. • The ethers decompose at near-critical temperatures. • Pulse-heating method with short residence times was used. -- Abstract: The critical temperatures T c and the critical pressures p c of dihexyl, dioctyl, and didecyl ethers have been measured. According to the measurements, the coordinates of the critical points are T c = (665 ± 7) K, p c = (1.44 ± 0.04) MPa for dihexyl ether, T c = (723 ± 7) K, p c = (1.19 ± 0.04) MPa for dioctyl ether, and T c = (768 ± 8) K, p c = (1.03 ± 0.03) MPa for didecyl ether. All the ethers studied degrade chemically at near-critical temperatures. A pulse-heating method applicable to measuring the critical properties of thermally unstable compounds has been used. The times from the beginning of a heating pulse to the moment of reaching the critical temperature were from 0.06 to 0.46 ms. The short residence times provide little decomposition of the substances in the course of the experiments. The critical properties of the ethers investigated in this work have been discussed together with those of methyl to butyl ethers. The experimental critical constants of the ethers have been compared with those estimated by the group-contribution methods of Wilson and Jasperson and Marrero and Gani. The Wilson/Jasperson method provides a better estimation of the critical temperatures and pressures of simple aliphatic ethers in comparison with the Marrero/Gani method if reliable normal boiling temperatures are used in the method of Wilson and Jasperson

Effect of electron beam irradiation on the biodegradability of aromatic aliphatic copolyester film and their blend with corn starch

Energy Technology Data Exchange (ETDEWEB)

Silva, Leonardo G. Andrade e; Poveda, Patricia N.S., E-mail: lgasilva@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Rezende, Maira L.; Rosa, Derval S. [Universidade Sao Francisco, Itatiba, SP (Brazil)

2009-07-01

Biodegradable and green plastics have been studied in the last years. The aim of this paper is to study the effect of electron beam irradiation on the biodegradability of aromatic aliphatic copolyester film and their blend with corn starch. The samples were irradiated at different doses 10 and 40 kGy in a linear accelerator. The biodegradability of the materials was evaluated by two methods: soil simulated and enzymatic. In the method enzymatic when it was used alpha-amylase, the irradiated samples presented faster biodegradation than the references non irradiated. The blend of aromatic aliphatic copolyester with corn starch (Ecobras{sup R}) irradiated presented a bigger biodegradability than the aromatic aliphatic copolyester (Ecoflex{sup R}) film in both methods studied. (author)

Highly Viscoelastic Reverse Wormlike Micellar Systems from a Mixture of Lecithin, Polyglycerol Fatty Acid Monoesters, and an Oil.

Science.gov (United States)

Hashizaki, Kaname; Imai, Miko; Yako, Shuhei; Tsusaka, Hitomi; Sakanishi, Yuichi; Saito, Yoshihiro; Fujii, Makiko

2017-09-01

We report new lecithin reverse wormlike micelles with high viscoelasticity formed using lecithin/polyglycerol fatty acid monoester (PGLFA)/oil systems. In this study, the influence of the amphiphilicity (i.e., hydrophile-lipophile balance, HLB) of PGLFA on the phase behavior and rheological properties of reverse wormlike micelles was investigated in detail. PGLFAs with degrees of polymerization of polyglycerol varying between 6-40 and constituent fatty acids with chains between 6-18 carbon atoms long were used. Partial phase diagrams of the lecithin/PGLFA/n-decane systems indicated that the appropriate PGLFA could change the lecithin/oil solution into a highly viscoelastic solution comprising reverse wormlike micelles. Rheological measurements showed that all systems that formed reverse wormlike micelles exhibited an unusual phenomenon called "shear-thickening". Furthermore, reverse wormlike micelles grew as the PGLFA concentration increased and the zero-shear viscosity (η 0 ) of the solution rapidly increased. Our results indicate that the magnitude of the maximum η 0 depends on the degree of polymerization of the constituent polyglycerol in the PGLFA, while the size of the reverse micellar region and the highly viscous region in the phase diagram depends on the HLB value of the PGLFA.

Formation of 3-MCPD Fatty Acid Esters from Monostearoyl Glycerol and the Thermal Stability of 3-MCPD Monoesters.

Science.gov (United States)

Zhao, Yue; Zhang, Yaqiong; Zhang, Zhongfei; Liu, Jie; Wang, Yi-Lin; Gao, Boyan; Niu, Yuge; Sun, Xiangjun; Yu, Liangli

2016-11-23

Formation of 3-monochloropropanediol (3-MCPD) esters from monostearoyl glycerol (MSG) was investigated under high temperature and low moisture conditions. Different organic and inorganic chlorides, including lindane, KCl, CaCl 2 , NaCl, MgCl 2 , AlCl 3 , CuCl 2 , MnCl 2 , SnCl 2 , ZnCl 2 , and FeCl 3 , were evaluated for their potential to react with MSG to form 3-MCPD and glycidyl esters at 120 and 240 °C using a UPLC-Q-TOF MS analysis. The results indicated that different chlorine compounds differed in their capacity to react with MSG and formed different products including 3-MCPD mono- and diesters, distearoylglycerol, and glycidyl esters. According to electron spin resonance (ESR) and Fourier transform infrared (FT-IR) spectroscopies, free radical mediated formation mechanisms involving either five-membered or six-membered cyclic acyloxonium free radicals (CAFR) from monoacylglycerol (MAG) were proposed. Tandem quadrupole-time-of-flight (Q-TOF) MS and MS/MS analyses confirmed the free radical mechanisms. In addition, the results from the present study showed that 3-MCPD monoester could be degraded upon thermal treatment and suggested a possible catalytic role of Fe 3+ under the experimental conditions.

Fully Biobased Unsaturated Aliphatic Polyesters from Renewable Resources : Enzymatic Synthesis, Characterization, and Properties

NARCIS (Netherlands)

Jiang, Yi; Alberda van Ekenstein, Gerhard; Woortman, Albert J. J.; Loos, Katja

2014-01-01

Fully biobased saturated and unsaturated aliphatic polyesters and oligoesters are successfully prepared by Candida antarctica lipase B (CALB)-catalyzed polycondensations of succinate, itaconate, and 1,4-butanediol. The effects of monomer substrates and polymerization methods on enzymatic

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

Directory of Open Access Journals (Sweden)

M. Onciu

2005-02-01

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

Influence of molecular weight on the fracture properties of aliphatic polyketone terpolymers

NARCIS (Netherlands)

Zuiderduin, W.C.J.; Homminga, D.S.; Homminga, D.S.; Huetink, Han; Gaymans, R.J.

2003-01-01

The influence of polymer molecular weight on the mechanical properties of aliphatic polyketones was investigated. The molecular weight varied from 100,000 to 300,000 g mol21. The crystallinity was found to be independent of polymer molecular weight, as was the glass transition temperature. The yield

Studies of the physical, yield and failure behavior of aliphatic polyketones

Science.gov (United States)

Karttunen, Nicole Renee

This thesis describes an investigation into the multiaxial yield and failure behavior of an aliphatic polyketone terpolymer. The behavior is studied as a function of: stress state, strain rate, temperature, and sample processing conditions. Results of this work include: elucidation of the behavior of a recently commercialized polymer, increased understanding of the effects listed above, insight into the effects of processing conditions on the morphology of the polyketone, and a description of yield strength of this material as a function of stress state, temperature, and strain rate. The first portion of work focuses on the behavior of a set of samples that are extruded under "common" processing conditions. Following this reference set of tests, the effect of testing this material at different temperatures is studied. A total of four different temperatures are examined. In addition, the effect of altering strain rate is examined. Testing is performed under pseudo-strain rate control at constant nominal octahedral shear strain rate for each failure envelope. A total of three different rates are studied. An extension of the first portion of work involves modeling the yield envelope. This is done by combining two approaches: continuum level and molecular level. The use of both methods allows the description of the yield envelope as a function of stress state, strain rate and temperature. The second portion of work involves the effects of processing conditions. For this work, additional samples are extruded with different shear and thermal histories than the "standard" material. One set of samples is processed with shear rates higher and lower than the standard. A second set is processed at higher and lower cooling rates than the standard. In order to understand the structural cause for changes in behavior with processing conditions, morphological characterization is performed on these samples. In particular, the effect on spherulitic structure is important. Residual

A Bioinspired Catalytic Aerobic Oxidative C–H Functionalization of Primary Aliphatic Amines: Synthesis of 1,2-Disubstituted Benzimidazoles

Science.gov (United States)

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

PcMtr, an aromatic and neutral aliphatic amino acid permease of Penicillium chrysogenum

NARCIS (Netherlands)

Trip, H; Evers, ME; Driessen, AJM

2004-01-01

The gene encoding an aromatic and neutral aliphatic amino acid permease of Penicillium chrysogenum was cloned, functionally expressed and characterized in Saccharomyces cerevisiae M4276. The permease, designated PcMtr, is structurally and functionally homologous to Mtr of Neurospora crassa, and

Aromatic-aliphatic copolyesters based on waste poly(ethylene terephthalate) and their biodegradability

Czech Academy of Sciences Publication Activity Database

Prokopová, I.; Vlčková, E.; Šašek, Václav; Náhlík, J.; Soukupová-Chaloupková, V.; Skolil, J.

-, 052 (2008), s. 1-9 ISSN 1618-7229 R&D Projects: GA ČR GA203/03/0508; GA ČR GA203/06/0528 Institutional research plan: CEZ:AV0Z50200510 Keywords : aromatic-aliphatic colpolyesters * rhodococcus erythropolis * biodegradability Subject RIV: EE - Microbiology, Virology Impact factor: 0.661, year: 2008

Conformational dynamics of semiflexibly bridged electron donor-acceptor systems comprising long aliphatic tails

NARCIS (Netherlands)

Bleisteiner, B.; Marian, T.; Schneider, S.; Brouwer, A.M.; Verhoeven, J.W.

2001-01-01

In continuation of our previous work on the conformational dynamics (harpooning mechanism) of semiflexibly bridged electron donor-acceptor systems we have studied a derivative with two long aliphatic chains tethered to the donor and acceptor moieties, respectively. The fitting of the time- and

Using of mass spectrum for prognosis of melting temperature of monatomic aliphatic spirits

International Nuclear Information System (INIS)

Vazhev, V. V.

2004-01-01

In present article researching possibility of prediction of melting temperature (MT) of monatomic aliphatic spirits with using mass-spectra as descriptors structure of molecules. Mass-spectra of 84 aliphatic spirits were used. Mass-spectra were preliminarily transformed on special formula before calculations for receiving work dates of descriptors. Calculations fulfilled with help of the computer program PROGROC. Quality of prediction characterized by coefficient of R-correlation between predicted and experimental dates MT and standard s-deviation. Coefficient of R-correlation between experimental and calculated dates account for 0.9785, standard s-deviation = 11.25 deg. C. Singly R and S for training and control excerpt equally 0.9789 and 11.31 deg. C, 0,9789 and 8.87 deg. C accordingly. Advantage of workable by us method lie in that, what on comparable with literature data of accuracy for prediction property is enough to have only mass-spectrum of substance

Degradation of halogenated aliphatic compounds by the ammonia- oxidizing bacterium Nitrosomonas europaea.

OpenAIRE

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),...

Pseudomonas sax genes overcome aliphatic isothiocyanate-mediated non-host resistance in Arabidopsis

Science.gov (United States)

Jun Fan; Casey Crooks; Gary Creissen; Lionel Hill; Shirley Fairhurst; Peter Doerner; Chris Lamb

2011-01-01

Most plant-microbe interactions do not result in disease; natural products restrict non-host pathogens. We found that sulforaphane (4-methylsulfinylbutyl isothiocyanate), a natural product derived from aliphatic glucosinolates, inhibits growth in Arabidopsis of non-host Pseudomonas bacteria in planta. Multiple sax genes (saxCAB/F/D/G) were identified in Pseudomonas...

Evaluation of Efficient and Practical Methods for the Preparation of Functionalized Aliphatic Trifluoromethyl Ethers.

Science.gov (United States)

Sokolenko, Taras M; Dronkina, Maya I; Magnier, Emmanuel; Yagupolskii, Lev M; Yagupolskii, Yurii L

2017-05-14

The "chlorination/fluorination" technique for aliphatic trifluoromethyl ether synthesis was investigated and a range of products with various functional groups was prepared. The results were compared with oxidative desulfurization-fluorination of xanthates with the same structure.

OCCUPATIONAL ASTHMA CAUSED BY A HARDENER CONTAINING AN ALIPHATIC AND A CYCLOALIPHATIC DIAMINE

NARCIS (Netherlands)

ALEVA, RM; AALBERS, R; KOETER, GH; DEMONCHY, JGR

An otherwise healthy 44-yr-old man experienced a serious attack of bronchial obstruction after working with resins and hardeners, releasing fumes of a mixture of an aliphatic and a cycloaliphatic diamine hardener. Eight hours after deliberate challenge with the hardener a large increase of airway

Evaluation of Efficient and Practical Methods for the Preparation of Functionalized Aliphatic Trifluoromethyl Ethers

Directory of Open Access Journals (Sweden)

Taras M. Sokolenko

2017-05-01

Full Text Available The “chlorination/fluorination” technique for aliphatic trifluoromethyl ether synthesis was investigated and a range of products with various functional groups was prepared. The results were compared with oxidative desulfurization-fluorination of xanthates with the same structure.

Estimating the octanol/water partition coefficient for aliphatic organic compounds using semi-empirical electrotopological index.

Science.gov (United States)

Souza, Erica Silva; Zaramello, Laize; Kuhnen, Carlos Alberto; Junkes, Berenice da Silva; Yunes, Rosendo Augusto; Heinzen, Vilma Edite Fonseca

2011-01-01

A new possibility for estimating the octanol/water coefficient (log P) was investigated using only one descriptor, the semi-empirical electrotopological index (I(SET)). The predictability of four octanol/water partition coefficient (log P) calculation models was compared using a set of 131 aliphatic organic compounds from five different classes. Log P values were calculated employing atomic-contribution methods, as in the Ghose/Crippen approach and its later refinement, AlogP; using fragmental methods through the ClogP method; and employing an approach considering the whole molecule using topological indices with the MlogP method. The efficiency and the applicability of the I(SET) in terms of calculating log P were demonstrated through good statistical quality (r > 0.99; s < 0.18), high internal stability and good predictive ability for an external group of compounds in the same order as the widely used models based on the fragmental method, ClogP, and the atomic contribution method, AlogP, which are among the most used methods of predicting log P.

Degradation of halogenated aliphatic compounds by the ammonia- oxidizing bacterium Nitrosomonas europaea.

Science.gov (United States)

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

High-resolution gas chromatographic analysis of polycyclic aromatic hydrocarbons and aliphatic hydrocarbons

International Nuclear Information System (INIS)

Perez, M.; Gonzalez, D.

1988-01-01

A study of the analysis by gas chromatography of aromatic polycyclic hydrocarbons and aliphatic hydrocarbons is presented. The separation has been carried out by glass and fused silica capillary column in two different polar stationary phases OV-1 and SE-54. The limitation and the advantages of the procedure are discussed in terms of separation, sensitivity and precision. (Author) 20 refs

Camphor-10-sulfonic acid catalyzed condensation of 2-naphthol with aromatic/aliphatic aldehydes to 14-aryl/alkyl-14H-dibenzo[a,j]xanthenes

Directory of Open Access Journals (Sweden)

Kundu Kshama

2014-01-01

Full Text Available (±-Camphor-10-sulfonic acid (CSA catalyzed condensation of 2-naphthol with both aliphatic/aromatic aldehydes at 80°C yielded 14-alkyl/aryl-dibenzoxanthenes as the sole product in high yields. However, the same condensation with benzaldehyde at 25°C afforded a mixture of intermediate 1,1-bis-(2-hydroxynaphthylphenylmethane and 14-phenyl-dibenzoxanthene while the condensation with aliphatic aldehydes at 25°C furnished the corresponding 14-alkyl-dibenzoxanthenes as the sole product. Moreover, condensation of 2-naphthol with aromatic/aliphatic aldehydes with low catalyst loading (2 mol% was greatly accelerated under microwave irradiation to afford the corresponding 14-aryl/alkyl-dibenzoxanthenes as the sole product in high yields.

A Quantitative Structure-Property Relationship (QSPR Study of Aliphatic Alcohols by the Method of Dividing the Molecular Structure into Substructure

Directory of Open Access Journals (Sweden)

Bin Cheng

2011-04-01

Full Text Available A quantitative structure–property relationship (QSPR analysis of aliphatic alcohols is presented. Four physicochemical properties were studied: boiling point (BP, n-octanol–water partition coefficient (lg POW, water solubility (lg W and the chromatographic retention indices (RI on different polar stationary phases. In order to investigate the quantitative structure–property relationship of aliphatic alcohols, the molecular structure ROH is divided into two parts, R and OH to generate structural parameter. It was proposed that the property is affected by three main factors for aliphatic alcohols, alkyl group R, substituted group OH, and interaction between R and OH. On the basis of the polarizability effect index (PEI, previously developed by Cao, the novel molecular polarizability effect index (MPEI combined with odd-even index (OEI, the sum eigenvalues of bond-connecting matrix (SX1CH previously developed in our team, were used to predict the property of aliphatic alcohols. The sets of molecular descriptors were derived directly from the structure of the compounds based on graph theory. QSPR models were generated using only calculated descriptors and multiple linear regression techniques. These QSPR models showed high values of multiple correlation coefficient (R > 0.99 and Fisher-ratio statistics. The leave-one-out cross-validation demonstrated the final models to be statistically significant and reliable.

Preparation and Properties of Some Novel Poly benzoxazine Containing Pendent Aliphatic Chains

International Nuclear Information System (INIS)

Agag, T.; Akelah, A.; Rehaband, A.; Mostafa, S.

2005-01-01

Poly benzoxazine as a newly developed type of phenolic resin has an excellent properties-process ability-price balance. Despite having the usual characteristics of the typical phenolic resins, such as heat resistance, good electronic properties and flame retardance, poly benzoxazine have additional advantageous characteristics superior to the typical phenolic. These characteristics include low melt viscosity of the monomers, no strong acid or basic catalysts needed for the polymerization, and no by-products evolved during the polymerization as well as near-zero shrinkage or expansion upon curing. However, the brittleness is considered the main disadvantage of this new class of thermoset, like all the conventional resins. In the current study, we have prepared a series of new monofunctional and bifunctional benzoxazine monomers from different long chain aliphatic amines, paraformaldehyde and various phenols, using solventless method. The structure of the novel monomers was confirmed by IR and 1H-NMR, indicating the presence of cyclic benzoxazine structure. The thermoset obtained by the thermal cure of benzoxazine monomers showed improved toughness with lower glass transition temperatures than the typical known types of poly benzoxazine due to the flexibilizing effect of the long aliphatic chains in the novel poly benzoxazine

Characterization of aliphatic and polycyclic aromatic hydrocarbons in environmental tobacco smokes

International Nuclear Information System (INIS)

Mohammad Fais Fadzil; Norhayati Mohd Tahir

2007-01-01

A study has been conducted to investigate the distribution of aliphatic and polycyclic aromatic hydrocarbons in Environmental Tobacco Smoke (ETS). ETS is the smoke that is present in the ambient air due to smoking of tobacco. Types of cigarettes (C1R1 and C6R1) were chosen based on a result of a simple survey carried out to determine the consumer choice of cigarette brand. In analyzing the ETS, volunteers were asked to smoke each brand of cigarette in a closed room and the ETS was then collected using the high Volume Air Sampler fitted with a glass fiber filter. Smoke samples from the glass fiber filter were then extracted using Ultrasonic Agitation and fractionated into aliphatic and aromatic fraction using silica-alumina column. Identification and quantification was done using gas chromatography with flame ionization detector. Results indicated the presence of n-alkanes in ETS, ranging from C 13 to C 36 with an odd to even carbon number predominance with Carbon Preference Index(CPI) values ranging from 3.34 to 4.90. Total identified resolved aliphatic hydrocarbons (TIRAH) concentration found in ETS ranged from 590 μg m -3 to 591 μg m -3 with the percentage of plant wax n-alkanes ranging from 61% to 64% of the TIRAH found in ETS samples. In source apportionment, CPI > 1 and high percentage of plant wax n-alkanes has generally been associated with the contribution of terrestrial plant source, thus this result indicates that even after curing process and smoking of tobacco, the overall signature of the source of n-alkanes is still preserved. Amount of PAHs detected in all ETS samples ranged from 11.7 ng m -3 to 56.1 ng m -3 . Results also indicated the presence of medium to high molecular weight PAHs with dominant presence of benzo(g, h, i)perylene compound. This result seems to support the contention that smoking process involves a high temperature burning with an oxygen deficient zone in the cigarette itself. Although the concentrations were low, the

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

Science.gov (United States)

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

2012-03-07

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.

Ru/Me-BIPAM-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes and α-Ketoesters

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Momoko Watanabe

2011-06-01

Full Text Available A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(arylmethanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM achieved excellent enantioselectivities.

Determinants of the microbial community structure of eutrophic, hyporheic river sediments polluted with chlorinated aliphatic hydrocarbons

NARCIS (Netherlands)

Hamonts, K.; Ryngaert, A.; Smidt, H.; Springael, D.; Dejonghe, W.

2014-01-01

Chlorinated aliphatic hydrocarbons (CAHs) often discharge into rivers as contaminated groundwater baseflow. As biotransformation of CAHs in the impacted river sediments might be an effective remediation strategy, we investigated the determinants of the microbial community structure of eutrophic,

Quantitative structure-activity relationships for toxicity and genotoxicity of halogenated aliphatic compounds: wing spot test of Drosophila melanogaster.

Science.gov (United States)

Chroust, Karel; Pavlová, Martina; Prokop, Zbynek; Mendel, Jan; Bozková, Katerina; Kubát, Zdenek; Zajícková, Veronika; Damborský, Jiri

2007-02-01

Halogenated aliphatic compounds were evaluated for toxic and genotoxic effects in the somatic mutation and recombination test employing Drosophila melanogaster. The tested chemicals included chlorinated, brominated and iodinated; mono-, di- and tri-substituted; saturated and unsaturated alkanes: 1,2-dibromoethane, 1-bromo-2-chloroethane, 1-iodopropane, 2,3-dichloropropene, 3-bromo-1-propene, epibromohydrin, 2-iodobutane, 3-chloro-2-methylpropene, 1,2,3-trichloropropane, 1,2-dichloroethane, 1,2-dichlorobutane, 1-chloro-2-methylpropane, 1,3-dichloropropane, 1,2-dichloropropane, 2-chloroethymethylether, 1-bromo-2-methylpropane and 1-chloropentane. N-methyl-N-nitrosourea served as the positive and distilled water as the negative control. The set of chemicals for the toxicological testing was selected by the use of statistical experiment design. Group of unsaturated aliphatic hydrocarbons were generally more toxic than saturated analogues. The genotoxic effect was observed with 14 compounds in the wing spot test, while 3 substances did not show any genotoxicity by using the wing spot test at 50% lethal concentration. The highest number of wing spots was observed in genotoxicity assay with 1-bromo-2-chloroethane, 1,2-dichloroethane, 1,2-dibromoethane and 1-iodopropane. Nucleophilic superdelocalizability calculated by quantum mechanics appears to be a good parameter for prediction of both toxicity and genotoxicity effects of halogenated aliphatic compounds.

Extraction-spectrophotometric determination of purine alkaloids in water solutions using aliphatic alcohols

Directory of Open Access Journals (Sweden)

Y. I. Korenman

2012-01-01

Full Text Available For extraction of caffeine, theobromin and theophylline from water solutions are applied aliphatic alcohols С3 – С9. Water concentrates analyzed method UF- spectrophotometry. Factors of distribution and extraction degree are calculated. Influence of length of a hydrocarbonic radical in a solvent and nature olecule salting-out agent on interphase distribution of alkaloids is studied. Dependence of quantitative characteristics extraction from number active groups in structure alkaloids is established.

Phase diagrams in blends of poly(3-hydroxybutyric acid with various aliphatic polyesters

Directory of Open Access Journals (Sweden)

2011-07-01

Full Text Available Phase behavior with immiscibility, miscibility, crystalline morphology, and kinetic analysis in blends of poly(3-hydroxybutyric acid (PHB with aliphatic polyesters such as poly(butylene adipate (PBA, poly(ethylene adipate (PEA, poly(trimethylene adipate (PTA, or poly(ethylene succinate (PESu, respectively, were explored mainly using differential scanning calorimeter (DSC and polarized-light optical microscopy (POM. Immiscibility phase behavior with reversible upper-critical-solution-temperature (UCST is common in the PHB/polyester blends. The polyester/polyester blend of PHB/PTA is partially miscible with no UCST in melt and amorphous glassy states within a composition range of PTA less than 50 wt%. The miscible crystalline/crystalline blend exhibits ring-banded spherulites at Tc = 50~100°C, with inter-ring spacing dependent on Tc. All immiscible or partially miscible PHB/polyester blends, by contrast, exhibit disrupted ringbanded spherulites or discrete spherical phase domains upon cooling from UCST to crystallization. The blends of PHB with all other aliphatic polyesters, such as PESu, PEA, PBA, etc. are only partially miscible or immiscible with an upper critical solution temperature (UCST at 180~221°C depending on blend composition. UCST with reversibility was verified.

Radiolytic crosslinking and chain scission in aliphatic and alkyl-aromatic polyamides: Pt. 2

International Nuclear Information System (INIS)

Lyons, B.J.; Glover, L.C. Jr.

1991-01-01

Regression analysis of the radiation parameters of nine aliphatic polyamides exposed to ionizing radiation leads to the conclusion that the decline in the ratio of chain scission to crosslinking in higher aliphatic polyamides is best related to the linear increase in the methylene content of, or the number of methylene groups in, the polyamide repeat unit. G(crosslink)[G(X)] and G(chain scission) [G(CS)] values, however, do not correlate well with either of these parameters. Rather it is found that the major determinant of yields [about 80-85% of the variation for G(X), 70% for G(CS)] is the number of hydrogen atoms or methylene groups in the amine residue. Although, logically, the yields of crosslinks and chain scissions in polyamides would be expected to tend to that of polyethylene as the number of methylene groups in the repeat unit increases, use of two models assuming an exponential trend to the G(X) value characteristic of polyethylene in the analysis did not provide better fits to the data than the simple linear model referred to above. Indeed, the assumption of a significant exponential trend factor led to a marked drop in the goodness of fit. (author)

Unravelling Protein-Protein Interaction Networks Linked to Aliphatic and Indole Glucosinolate Biosynthetic Pathways in Arabidopsis

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Sebastian J. Nintemann

2017-11-01

Full Text Available Within the cell, biosynthetic pathways are embedded in protein-protein interaction networks. In Arabidopsis, the biosynthetic pathways of aliphatic and indole glucosinolate defense compounds are well-characterized. However, little is known about the spatial orchestration of these enzymes and their interplay with the cellular environment. To address these aspects, we applied two complementary, untargeted approaches—split-ubiquitin yeast 2-hybrid and co-immunoprecipitation screens—to identify proteins interacting with CYP83A1 and CYP83B1, two homologous enzymes specific for aliphatic and indole glucosinolate biosynthesis, respectively. Our analyses reveal distinct functional networks with substantial interconnection among the identified interactors for both pathway-specific markers, and add to our knowledge about how biochemical pathways are connected to cellular processes. Specifically, a group of protein interactors involved in cell death and the hypersensitive response provides a potential link between the glucosinolate defense compounds and defense against biotrophic pathogens, mediated by protein-protein interactions.

Modification of eucalyptus pulp fiber using silane coupling agents with aliphatic side chains of different length

Science.gov (United States)

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...

Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

International Nuclear Information System (INIS)

Wang, Sujing; Li, Jing

2015-01-01

As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn 2 S 2 (bza) (1), Zn 2 S 2 (mbza) (2), Zn 2 S 2 (fbza) (3), Zn 2 S 2 (pca) (4), and Zn 2 S 2 (thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn 2 S 2 (L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy

Syntheses of Enantiopure Aliphatic Secondary Alcohols and Acetates by Bioresolution with Lipase B from Candida antarctica

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Richele P. Severino

2012-07-01

Full Text Available The lipase B from Candida antarctica (Novozym 435^®, CALB efficiently catalyzed the kinetic resolution of some aliphatic secondary alcohols: (±-4-methylpentan-2-ol (1, (±-5-methylhexan-2-ol (3, (±-octan-2-ol (4, (±-heptan-3-ol (5 and (±-oct-1-en-3-ol (6. The lipase showed excellent enantioselectivities in the transesterifications of racemic aliphatic secondary alcohols producing the enantiopure alcohols (>99% ee and acetates (>99% ee with good yields. Kinetic resolution of rac-alcohols was successfully achieved with CALB lipase using simple conditions, vinyl acetate as acylating agent, and hexane as non-polar solvent.

Two-dimensional inorganic–organic hybrid semiconductors composed of double-layered ZnS and monoamines with aromatic and heterocyclic aliphatic rings: Syntheses, structures, and properties

Energy Technology Data Exchange (ETDEWEB)

Wang, Sujing; Li, Jing, E-mail: jingli@rutgers.edu

2015-04-15

As an addition to the II–VI based inorganic–organic hybrid semiconductor family, five new two-dimensional (2D) double-layered structures have been synthesized employing monoamines with different aromatic or heterocyclic aliphatic rings. Zn{sub 2}S{sub 2}(bza) (1), Zn{sub 2}S{sub 2}(mbza) (2), Zn{sub 2}S{sub 2}(fbza) (3), Zn{sub 2}S{sub 2}(pca) (4), and Zn{sub 2}S{sub 2}(thfa) (5) (bza=benzylamine, mbza=4-methoxybenzylamine, fbza=4-flurobenzylamine, pca=3-picolylamine, and thfa=tetrahydrofurfurylamine) are prepared by solvothermal reactions and characterized by different analytical methods, including powder X-ray diffraction, optical diffuse reflection, thermogravimetric analysis and photoluminescence spectroscopy. The powder X-ray diffraction patterns show that all five compounds adopt 2D double-layered structures. Optical diffuse reflectance spectra of these compounds suggest that they have notably lower band gaps than those of the similar compounds composed of aliphatic alkyl amines. Their photoluminescence properties and thermal stability are also analyzed. - Graphical abstract: Five new members of two-dimensional double-layered 2D-Zn{sub 2}S{sub 2}(L) (L=Ligand) structures employing monoamines with different aromatic or heterocyclic aliphatic rings have been designed, synthesized, and characterized. - Highlights: • A new sub-family of II-VI based hybrid semiconductors are designed, synthesized, and structurally characterized using amines with aromatic or aliphatic cyclic rings. • These compounds have notably lower band gaps than those made of aliphatic alkyl amines, greatly broadening the range of band gaps of this material family. • They emit strongly with systematically tunable emission intensity and energy.

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

Science.gov (United States)

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.

Aliphatic and polycyclic aromatic hydrocarbons in Gulf of Trieste sediments (northern Adriatic): potential impacts of maritime traffic.

Science.gov (United States)

Bajt, Oliver

2014-09-01

The Gulf of Trieste (northern Adriatic) is one of the most urbanized and industrialized areas in the northern Adriatic, with intense maritime traffic experienced at multiple ports. The impact of maritime traffic on contamination by hydrocarbons in this area was assessed. Concentrations of hydrocarbons were higher near the expected contamination sources and still elevated in the adjacent offshore areas. Aliphatic hydrocarbons were mainly of petrogenic origin, with some contribution of biogenic origin. A continuous contamination by aliphatic hydrocarbons and degradation processes were hypothesized. Concentrations of total polycyclic aromatic hydrocarbons (PAH) were generally greater near the contamination sources. Compared to the prevailing pyrolytic origin, the petrogenic PAH origin seemed to be less important, but not negligible. Results revealed that intensive maritime traffic is a probable source of contamination by hydrocarbons in the investigated area, which is largely limited to areas near the contamination sources.

A sol-gel based solid phase microextraction fiber for the analysis of aliphatic alcohols in apple juices.

Science.gov (United States)

Farhadi, Khalil; Maleki, Ramin; Tahmasebi, Raheleh

2010-01-01

A new fiber based on titania-chitin sol-gel coated on a silver wire for the headspace solid phase microextraction of aliphatic alcohols from apple juice samples was developed. The influences of fiber coating composition and microextraction conditions (extraction temperature, extraction time, and ionic strength of the sample matrix) on the fiber performance were investigated. Also, the influence of temperature and time on desorption of analytes from fiber were studied. Under the optimized conditions, a porous fiber with a high extraction capacity and good thermal stability (up to 250 degrees C) was obtained. The proposed headspace solid-phase microextraction-GC method was successfully used for the analysis of aliphatic alcohols in apple juice and concentrate samples. The recovery values were from 92.8 to 98.6%. The RSD (n=5) for all analytes were below 7.8%.

Metal-free synthesis of novel biobased dihydroxyl-terminated aliphatic polyesters as building blocks for thermoplastic polyurethanes

NARCIS (Netherlands)

Tang, D.; Noordover, B.A.J.; Sablong, R.J.; Koning, C.E.

2011-01-01

Using the organic compound 1,5,7-triazabicyclo[ 4.4.0]dec-5-ene (TBD) as a catalyst for step-growth polymerization, a series of well-defined hydroxyl-telechelic renewable aliphatic polyesters (including poly(1,3-propylene adipate); poly(1,4-butylene adipate); poly(1,12-dodecylene sebacate); and

Vapour pressures and enthalpies of vapourization of a series of the linear aliphatic nitriles

International Nuclear Information System (INIS)

Emel'yanenko, Vladimir N.; Verevkin, Sergey P.; Koutek, Bohumir; Doubsky, Jan

2005-01-01

Vapour pressures and the molar enthalpies of vapourization ΔlgHm-bar of the linear aliphatic nitriles C 7 -C 17 have been determined by the transpiration method. Kovat's indices of these compounds were measured by capillary gas-chromatography. A linear correlation of enthalpies of vapourization ΔlgHm-bar at T=298.15 K of the nitriles studied with the Kovats indices has been found

Amperometric detection and electrochemical oxidation of aliphatic amines and ammonia on silver-lead oxide thin-film electrodes

Energy Technology Data Exchange (ETDEWEB)

Ge, Jisheng [Iowa State Univ., Ames, IA (United States)

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.

Laboratory Study of Aliphatic Organic Spectral Signatures and Applications to Ceres and Primitive Asteroids

Science.gov (United States)

Kaplan, H. H.; Milliken, R.

2017-12-01

Aliphatic organics were recently discovered on the surface of Ceres with Dawn's Visible and InfraRed (VIR) mapping spectrometer, which has implications for prebiotic chemistry of Ceres and other asteroids. An absorption in the spectrum at 3.4 µm was used to identify and provide initial estimates of the amount of organic material. We have studied the 3.4 µm absorption in reflectance spectra of bulk rock and meteorite powders and isolated organic materials in the NASA RELAB facility at Brown University to determine how organic composition and abundance affects absorption strength. Reflectance spectra of insoluble organic matter (IOM) extracted from carbonaceous chondrites were measured from 0.35 - 25 µm. These IOM have known elemental (H, C, N, O) and isotopic compositions that were compared with spectral properties. Bulk meteorites were measured as chips and particulates over the same wavelength range. Despite overall low reflectance values (albedo IOM samples, specifically those with a H/C ratio greater than 0.4. The absorption strength (band depth) increases with increasing H/C ratio, which corroborates similar findings in our previous study of sedimentary rocks and isolated kerogens. The absorption strength in the bulk meteorites reflects both H/C of the IOM and the concentration of IOM in the inorganic (mineral) matrix. Overlapping absorptions from carbonates and phyllosilicates (OH/H2O) can also influence the aliphatic organic bands in bulk rocks and meteorites. This laboratory work provides a foundation that can be used to constrain the composition of Ceres' aliphatic organic matter using band depth as a proxy for H/C. Reflectance spectra collected for this work will also be used to model the Dawn VIR data and obtain abundance and H/C estimates assuming that the organic material on Ceres' surface is similar to carbonaceous chondrite IOM. These spectra and findings can aid interpretation of reflectance data from Ceres and other asteroid missions, such as

Hofmeister effect on the interfacial free energy of aliphatic and aromatic surfaces studied by chemical force microscopy.

Science.gov (United States)

Patete, Jonathan; Petrofsky, John M; Stepan, Jeffery; Waheed, Abdul; Serafin, Joseph M

2009-01-15

This work describes chemical force microscopy (CFM) studies of specific-ion effects on the aqueous interfacial free energy of hydrophobic monolayers. CFM measurements allow for the characterization of interfacial properties on length scales below 100 nm. The ions chosen span the range of the Hofmeister series, from the kosmotropic Na(2)SO(4) to the chaotropic NaSCN. The salt concentrations used are typical of many laboratory processes such as protein crystallization, 2-3 M. Both aliphatic (terminal methyl) and aromatic (terminal phenyl) monolayers were examined, and rather pronounced differences were observed between the two cases. The specific-ion dependence of the aliphatic monolayer closely follows the Hofmeister series, namely the chaotropic ions lowered the interfacial free energy and the kosmotropic ions increased the interfacial free energy. However, the aromatic monolayer had significant deviations from the Hofmeister series. Possible origins for this difference are discussed.

Cloning of genes related to aliphatic glucosinolate metabolism and the mechanism of sulforaphane accumulation in broccoli sprouts under jasmonic acid treatment.

Science.gov (United States)

Guo, Liping; Yang, Runqiang; Gu, Zhenxin

2016-10-01

Cytochrome P450 79F1 (CYP79F1), cytochrome P450 83A1 (CYP83A1), UDP-glucosyltransferase 74B1 (UGT74B1), sulfotransferase 18 (ST5b) and flavin-containing monooxygenase GS-OX1 (FMOGS - OX1 ) are important enzymes in aliphatic glucosinolate biosynthesis. In this study, their full-length cDNA in broccoli was firstly cloned, then the mechanism of sulforaphane accumulation under jasmonic acid (JA) treatment was investigated. The full-length cDNA of CYP79F1, CYP83A1, UGT74B1, ST5b and FMOGS - OX1 comprised 1980, 1652, 1592, 1378 and 1623 bp respectively. The increase in aliphatic glucosinolate accumulation in broccoli sprouts treated with JA was associated with elevated expression of genes in the aliphatic glucosinolate biosynthetic pathway. Application of 100 µmol L(-1) JA increased myrosinase (MYR) activity but did not affect epithiospecifier protein (ESP) activity in broccoli sprouts, which was supported by the expression of MYR and ESP. Sulforaphane formation in 7-day-old sprouts treated with 100 µmol L(-1) JA was 3.36 and 1.30 times that in the control and 300 µmol L(-1) JA treatment respectively. JA enhanced the accumulation of aliphatic glucosinolates in broccoli sprouts via up-regulation of related gene expression. Broccoli sprouts treated with 100 µmol L(-1) JA showed higher sulforphane formation than those treated with 300 µmol L(-1) JA owing to the higher glucoraphanin content and myrosinase activity under 100 µmol L(-1) JA treatment. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Sodium hypochlorite oxidation of petroleum aliphatic contaminants in calcareous soils.

Science.gov (United States)

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Hydrolytic And Enzymatic Degradation Characteristics Of Biodegradable Aliphatic Polysters

Institute of Scientific and Technical Information of China (English)

LI Suming

2004-01-01

Aliphatic polyesters, especially those derived from lactide (PLA), glycolide (PGA) and ε-caprolactone (PCL), are being investigated worldwide for applications in the field of surgery (suture material, devices for internal bone fracture fixation), pharmacology (sustained drug delivery systems), and tissue engineering (scaffold for tissue regeneration) [1,2]. This is mainly due to their good biocompatibility and variable degradability. These polymers present also a growing interest for environmental applications in agriculture (mulch films) and in our everyday life (packaging material)as the development of biodegradable materials is now considered as one of the potential solutions to the problem of plastic waste management.For both biomedical and environmental applications, it is of major importance to understand the degradation characteristics of the polymers. The hydrolytic degradation of aliphatic polyesters has been investigated by many research groups. Our group has shown that degradation of PLAGA large size devices is faster inside than at the surface. This heterogeneous degradation is due to the autocatalytic effect of carboxylic endgroups formed by ester bond cleavage. Moreover,degradation-induced morphological and compositional changes were also elucidated. In the case of PCL, the hydrolytic degradation is very slow due to its hydrophobicity and crystallinity.The enzymatic degradation of these polymers has been investigated by a number of authors. A specific enzyme, proteinase K, has been shown to have significant effects on PLA degradation. This enzyme preferentially degrade L-lactate units as opposed to D-lactate ones, amorphous zones as opposed to crystalline ones [3]. The enzymatic degradation of PCL polymers has also been investigated. A number of lipase-type enzymes were found to significantly accelerate the degradation of PCL despite its high crystallinity. In the case of PLA/PCL blends, the two components exhibited well separated crystalline domains

Vapour pressure and enthalpy of vaporization of aliphatic poly-amines

International Nuclear Information System (INIS)

Efimova, Anastasia A.; Emel'yanenko, Vladimir N.; Verevkin, Sergey P.; Chernyak, Yury

2010-01-01

Molar enthalpies of vaporization of aliphatic poly-amines: 1,4-dimethylpiperazine [106-58-1], 1-(2-aminoethyl)-piperazine, [140-31-8], 1-(2-aminoethyl)-4-methyl-piperazine [934-98-5], and triethylenetetramine [112-24-3] were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. A large number of the primary experimental results on temperature dependences of vapour pressures of the parent compounds have been collected from the literature and have been treated uniformly in order to derive vaporization enthalpies of poly-amines at the reference temperature 298.15 K. An internal consistency check was performed on enthalpy of vaporization values for poly-amines studied in this work.

Localized aliphatic organic material on the surface of Ceres

Science.gov (United States)

De Sanctis, M. C.; Ammannito, E.; McSween, H. Y.; Raponi, A.; Marchi, S.; Capaccioni, F.; Capria, M. T.; Carrozzo, F. G.; Ciarniello, M.; Fonte, S.; Formisano, M.; Frigeri, A.; Giardino, M.; Longobardo, A.; Magni, G.; McFadden, L. A.; Palomba, E.; Pieters, C. M.; Tosi, F.; Zambon, F.; Raymond, C. A.; Russell, C. T.

2017-02-01

Organic compounds occur in some chondritic meteorites, and their signatures on solar system bodies have been sought for decades. Spectral signatures of organics have not been unambiguously identified on the surfaces of asteroids, whereas they have been detected on cometary nuclei. Data returned by the Visible and InfraRed Mapping Spectrometer on board the Dawn spacecraft show a clear detection of an organic absorption feature at 3.4 micrometers on dwarf planet Ceres. This signature is characteristic of aliphatic organic matter and is mainly localized on a broad region of ~1000 square kilometers close to the ~50-kilometer Ernutet crater. The combined presence on Ceres of ammonia-bearing hydrated minerals, water ice, carbonates, salts, and organic material indicates a very complex chemical environment, suggesting favorable environments to prebiotic chemistry.

A bioinspired catalytic aerobic oxidative C-H functionalization of primary aliphatic amines: synthesis of 1,2-disubstituted benzimidazoles.

Science.gov (United States)

Nguyen, Khac Minh Huy; Largeron, Martine

2015-09-01

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. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of Creative Commons Attribution NonCommercial-NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

Efficient 'One Pot' Nitro Reduction-Protection of γ-Nitro Aliphatic Methyl Esters

OpenAIRE

Díaz-Coutiño, Francisco D.; Escalante, Jaime

2009-01-01

A simple and efficient protocol has been developed for the direct conversion of γ-nitro aliphatic methyl esters to N-(tert-butoxycarbonyl)amine methyl esters using NH4+HCO2- and Pd/C in the presence of (Boc)2O. There was a significant decrease in the reaction time under these conditions, increased yields and the purity of the products using this 'one pot' procedure. Un protocolo simple y eficiente de síntesis ha sido desarrollado para la conversión directa de metil ésteres de γ-nitro alifá...

Evaluation of 10 aliphatic halogenated hydrocarbons in the mouse bone marrow micronucleus test.

Science.gov (United States)

Crebelli, R; Carere, A; Leopardi, P; Conti, L; Fassio, F; Raiteri, F; Barone, D; Ciliutti, P; Cinelli, S; Vericat, J A

1999-03-01

Ten halogenated aliphatic hydrocarbons (carbon tetrachloride, 1-chlorohexane, 2,3-dichlorobutane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,3-dichloropropane, hexachloroethane, 1,1,2-trichloroethane, 1,2,3-trichloropropane and 1,1,3-trichloropropene), previously assayed in genetic assays in fungi, were evaluated in the mouse bone marrow micronucleus test in order to assess their genotoxicity in vivo. All chemicals were administered once i.p. at 40 and 70-80% of their respective LD50 to male and female CD-1 mice, 24 and 48 h before killing. All treatments produced evident clinical symptoms, but no marked depression of bone marrow proliferation. No statistically significant increases in the incidence of micronucleated polychromatic erythrocytes over the control values were observed at any sampling time with any of the 10 halogenated hydrocarbons assayed. The comparison of the results obtained in this study with the findings provided by in vitro micronucleus assays on the same chemicals, reported by other authors, indicate that mouse bone marrow is weakly sensitive to the genotoxic effects induced by halogenated hydrocarbons in other test systems. This suggests that the role of such an assay in carcinogen screening may be questionable for this chemical class. An examination of mouse bone marrow micronucleus test results with the halogenated aliphatic hydrocarbons classified as carcinogens by IARC supports this conclusion.

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

Directory of Open Access Journals (Sweden)

Bonaventure Gustavo

2009-11-01

Full Text Available Abstract 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

Synthesis of Scutellarein Derivatives with a Long Aliphatic Chain and Their Biological Evaluation against Human Cancer Cells

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Guanghui Ni

2018-02-01

Full Text Available Scutellarin is the major active flavonoid extracted from the traditional Chinese herbal medicine Erigeron breviscapus (Vant. Hand-Mazz., which is widely used in China. Recently, accumulating evidence has highlighted the potential role of scutellarin and its main metabolite scutellarein in the treatment of cancer. To explore novel anticancer agents with high efficiency, a series of new scutellarein derivatives with a long aliphatic chain were synthesized, and the antiproliferative activities against Jurkat, HCT-116 and MDA-MB-231 cancer cell lines were assessed. Among them, compound 6a exhibited the strongest antiproliferative effects on Jurkat (IC50 = 1.80 μM, HCT-116 (IC50 = 11.50 μM and MDA-MB-231 (IC50 = 53.91 μM. In particular, 6a even showed stronger antiproliferative effects than the positive control NaAsO2 on Jurkat and HCT-116 cell lines. The results showed that a proper long aliphatic chain enhanced the antiproliferative activity of scutellarein.

Synthesis of Scutellarein Derivatives with a Long Aliphatic Chain and Their Biological Evaluation against Human Cancer Cells.

Science.gov (United States)

Ni, Guanghui; Tang, Yanling; Li, Minxin; He, Yuefeng; Rao, Gaoxiong

2018-02-01

Scutellarin is the major active flavonoid extracted from the traditional Chinese herbal medicine Erigeron breviscapus (Vant.) Hand-Mazz., which is widely used in China. Recently, accumulating evidence has highlighted the potential role of scutellarin and its main metabolite scutellarein in the treatment of cancer. To explore novel anticancer agents with high efficiency, a series of new scutellarein derivatives with a long aliphatic chain were synthesized, and the antiproliferative activities against Jurkat, HCT-116 and MDA-MB-231 cancer cell lines were assessed. Among them, compound 6a exhibited the strongest antiproliferative effects on Jurkat (IC 50 = 1.80 μM), HCT-116 (IC 50 = 11.50 μM) and MDA-MB-231 (IC 50 = 53.91 μM). In particular, 6a even showed stronger antiproliferative effects than the positive control NaAsO₂ on Jurkat and HCT-116 cell lines. The results showed that a proper long aliphatic chain enhanced the antiproliferative activity of scutellarein.

Effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds using a modified QSAR model.

Science.gov (United States)

Lim, Seung Joo; Fox, Peter

2014-02-01

The effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds were investigated using a modified half life equation. The potential future pharmaceutical compounds investigated were approximately 2000 pharmaceutical drugs currently undergoing the United States Food and Drug Administration (US FDA) testing. EPI Suite (BIOWIN) model estimates the fates of compounds based on the biodegradability under aerobic conditions. While BIOWIN considered the biodegradability of a compound only, the half life equation used in this study was modified by biodegradability, sorption and cometabolic oxidation. It was possible that the potential future pharmaceutical compounds were more accurately estimated using the modified half life equation. The modified half life equation considered sorption and cometabolic oxidation of halogenated aromatic/aliphatics and nitrogen(N)-heterocyclic aromatics in the sub-surface, while EPI Suite (BIOWIN) did not. Halogenated aliphatics in chemicals were more persistent than halogenated aromatics in the sub-surface. In addition, in the sub-surface environment, the fates of organic chemicals were much more affected by halogenation in chemicals than by nitrogen(N)-heterocyclic aromatics. © 2013.

Occurrence and sources of aliphatic hydrocarbons in surface soils from Riyadh city, Saudi Arabia

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Ahmed I. Rushdi

2013-01-01

Full Text Available Soil particles contain a variety of anthropogenic and natural organic components derived from many sources such as industrial and traffic fossil fuel emissions and terrestrial biota. The organic contents of soil and sand from the Arabian region have not fully characterized. Thus, samples of fine soil particles (sieved to <125 μM were collected from the Riyadh area in November 2006 (late summer and February 2007 (late winter. The samples were extracted with a mixture of dichloromethane/hexane and analyzed by gas chromatography–mass spectroscopy (GCMS in order to characterize the chemical composition and sources of aliphatic hydrocarbons. The results showed that both anthropogenic and natural biogenic inputs were the major sources of the aliphatic hydrocarbons in these extracts. Vehicular emission products and discarded plastics were the major anthropogenic sources in the fine particles of the soils and ranged from 64% to 96% in November 2006 and from 70% to 92% in February 2007. Their tracers were n-alkanes, hopanes, sterane, plasticizers and UCM. Vegetation was also a major natural source of hydrocarbon compounds in samples ranging from ∼0% to18% in November 2006 and from 1% to 13% in February 2007 and included n-alkanes and triterpenoids.

Assay of Aliphatic Phthalates in Polymer Products by Sensitive Polarographic Method: Health and Environmental Issue

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Munawar Saeed

2010-06-01

Full Text Available A faster, simpler and sensitive method was developed for determination of aliphatic phthalates using differential pulse polarography (DPP as standard technique. The choice and concentration of base electrolyte, solvent, initial potential, effect of water addition and interference by other phthalates were the main parameters to optimize for enhancement of peak current and to obtain well-defined polarogram with lower background current using 1.3 x 10-4 M di-butyl phthalate (DBP solution. Best results were obtained in the presence of tetra methyl ammonium bromide (TMAB as electrolyte in methanol solvent with initial potential, -1.4 V. A linear calibration plot was observed in the range of 3 x 10-7 – 1.6 x 10-4 M DBP solution as aliphatic phthalates with lower detection limit of 5.9 x 10-8 M and linear regression coefficient of 0.9987. The developed polarographic method was successfully applied for analysis of aliphtaic phthalates in various samples of locally available polymer products such as baby toys, nipples, teethers, infusion blood bags and shopping bags. The results of the current method were compared with those obtained by a reported method and good agreement was found between them.

NMR studies on the mechanism of structural destabilization of the globular proteins and DNA by aliphatic alcohols

International Nuclear Information System (INIS)

Lubas, B.; Witman, B.; Wieniewska, T.; Soltysik, M.

1977-01-01

The concept that the mechanism of structural destabilization of the biologically active macromolecules by typical denaturing agents should find a reflection in the NMR spectra of the denaturants themselves has been followed by proton NMR for some aliphatic alcohols in the system containing the serum albumin of DNA. (author)

Preparation and characterization of aliphatic diphenyl esters intended as precursors for polyesters

DEFF Research Database (Denmark)

Hvilsted, S.; Andruzzi, F.; Cerrai, P.

1991-01-01

An extensive number of aliphatic diphenyl esters, C6H5OOC(CH2)nCOOC6H5 (n = O,...,8,10,11,12,14), have been prepared in pure form. The crystalline melting points these esters exhibit an odd-even temperature behaviour, with the higher-melting even series (n even) displaying a minimum for n = 8 while...... based on similar data from phenyl esters, interpreted as the results of an apparent macrocyclic conformation of the larger diphenyl esters. High-performance size exclusion chromatography (s.e.c.) of diphenyl esters, phenyl esters, aromatic and linear hydrocarbons in tetrahydrofuran, toluene...

Temporal variations in natural attenuation of chlorinated aliphatic hydrocarbons in eutrophic river sediments impacted by a contaminated groundwater plume

NARCIS (Netherlands)

Hamonts, K.; Kuhn, T.; Vos, J.; Maesen, M.; Kalka, H.; Smidt, H.; Springael, D.; Meckenstock, R.U.; Dejonghe, W.

2012-01-01

Chlorinated aliphatic hydrocarbons (CAHs) often discharge into rivers as contaminated groundwater base flow. Biotrans formation, sorption and dilution of CAHs in the impacted river sediments have been reported to reduce discharge, but the effect of temporal variations in environmental conditions on

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

Science.gov (United States)

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. Copyright © 2013 Elsevier Ltd. All rights reserved.

EFSA ; Scientific Opinion on Flavouring Group Evaluation 94, Revision 1 (FGE.94Rev1): Consideration of aliphatic amines and amides evaluated in an addendum to the group of aliphatic and aromatic amines and amides evaluated by the JECFA (68th meeting)

DEFF Research Database (Denmark)

Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 12 aliphatic amines and amides evaluated by the JECFA at the 68th meeting in 2007. This revision of the consideration is made due to additional toxicity data available for two...

Structural characterisation of aliphatic, non-hydrolyzable biopolymers in freshwater algae and a leaf cuticle by ruthenium tetroxide degradation

NARCIS (Netherlands)

Sinninghe Damsté, J.S.; Schouten, S.; Moerkerken, P.; Gelin, F.; Baas, M.; Leeuw, J.W. de

1998-01-01

Aliphatic, non-hydrolyzable biopolymers were subjected to RuO4-oxidation in order to examine the potential of this method in revealing details on their structures. The method was tested on model compounds first and found to cleave alkyl chains of aromatic moieties, double bonds and ether bonds.

Vapor pressure and enthalpy of vaporization of linear aliphatic alkanediamines

International Nuclear Information System (INIS)

Pozdeev, Vasiliy A.; Verevkin, Sergey P.

2011-01-01

Highlights: → We measured vapor pressure of diamines H 2 N-(CH 2 ) n -NH 2 with n = 3 to 12. → Vaporization enthalpies at 298 K were derived. → We examined consistency of new and available in the literature data. → Enthalpies of vaporization show linear dependence on numbers n. → Enthalpies of vaporization correlate linearly with Kovat's indices. - Abstract: Vapor pressures and the molar enthalpies of vaporization of the linear aliphatic alkanediamines H 2 N-(CH 2 ) n -NH 2 with n = (3 to 12) have been determined using the transpiration method. A linear correlation of enthalpies of vaporization (at T = 298.15 K) of the alkanediamines with the number n and with the Kovat's indices has been found, proving the internal consistency of the measured data.

N-hydroxysuccinimide-mediated photoelectrooxidation of aliphatic alcohols based on cadmium telluride nanoparticles decorated graphene nanosheets

International Nuclear Information System (INIS)

Navaee, Aso; Salimi, Abdollah

2013-01-01

A simple nonenzymatic electrochemical protocol is proposed for the oxidation of aliphatic alcohols using formed N-hydroxysuccinimide (NHS) radical cation on the graphene nanosheets/L-cysteine/cadmium telluride quantum dot (QD) nanocomposite (GNs/Cys/CdTe) modified glassy carbon (GC) electrode. At first, graphene oxide (GO) is chemically synthesized from graphite after which Cys is covalently functionalized to GO through formation of amide bonds between carboxylic acid groups of GO and amine groups of Cys. The resulting GNs/Cys is used as a capping agent to synthesize CdTe QD nanoparticles. After the characterization of the as-made nanocomposite which confirmed the successful attachment of CdTe nanoparticles to the GNs, the ability of the GNs/Cys/CdTe modified GC electrode toward the nonenzymatic ethanol electrooxidation is examined in the presence of NHS as an effective mediating system. Our results revealed that the proposed system possess a good activity to NHS electrooxidation and subsequently, ethanol oxidation. Moreover, the GNs/Cys/CdTe modified electrode displayed a significant photoelectrocatalytic activity toward the ethanol oxidation upon illumination by visible light. The photoactive GNs/Cys/CdTe nanohybrid presented here showing favorable photoelectrochemical features for nonenzymatic aliphatic alcohols oxidation may hold great promise to the development of electrochemical sensors and biofuel cells

Screening and Quantification of Aliphatic Primary Alkyl Corrosion Inhibitor Amines in Water Samples by Paper Spray Mass Spectrometry.

Science.gov (United States)

Jjunju, Fred P M; Maher, Simon; Damon, Deidre E; Barrett, Richard M; Syed, S U; Heeren, Ron M A; Taylor, Stephen; Badu-Tawiah, Abraham K

2016-01-19

Direct analysis and identification of long chain aliphatic primary diamine Duomeen O (n-oleyl-1,3-diaminopropane), corrosion inhibitor in raw water samples taken from a large medium pressure water tube boiler plant water samples at low LODs (corrosion inhibitors in an industrial water boiler plant and other related samples in the water treatment industry. This approach was applied for the analysis of three complex water samples including feedwater, condensate water, and boiler water, all collected from large medium pressure (MP) water tube boiler plants, known to be dosed with varying amounts of polyamine and amine corrosion inhibitor components. Polyamine chemistry is widely used for example in large high pressure (HP) boilers operating in municipal waste and recycling facilities to prevent corrosion of metals. The samples used in this study are from such a facility in Coventry waste treatment facility, U.K., which has 3 × 40 tonne/hour boilers operating at 17.5 bar.

A microanalytical method for ammonium and short-chain primary aliphatic amines using precolumn derivatization and capillary liquid chromatography.

Science.gov (United States)

Moliner-Martínez, Y; Herráez-Hernández, R; Campíns-Falcó, P

2007-09-14

A new microscale method is presented for the determination of ammonium and primary short-chain aliphatic amines (methylamine, ethylamine, propylamine, n-butylamine and n-pentylamine) in water. The assay uses precolumn derivatization with the reagent o-phthaldialdehyde (OPA) in combination with the thiol N-acetyl-L-cysteine (NAC), and capillary liquid chromatography with UV detection at 330 nm. The described method is very simple and rapid as no preconcentration of the analytes is necessary, and the volume of sample required is only 0.1 mL. Under the proposed conditions good linearity has been obtained up to a concentration of the analytes of 10.0 mgL(-1), the limits of detection being of 8-50 microgL(-1). No matrix effect was found, and recoveries between 97 and 110% were obtained. The precision of the method was good, and the achieved variation coefficients were below 12%. The reliability of the proposed approach has been tested by analyzing a microsample of fogwater collected from leaf surfaces.

Simultaneous determination of aliphatic hydrocarbons, PCBs and PCTs in pork liver by gas chromatography

Energy Technology Data Exchange (ETDEWEB)

Gonzalez-Barros, C [Dept. de Quimica Analitica, Nutricion y Bromatologia, Area Nutricion y Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain); Alvarez Pineiro, M E [Inst. de Investigacion y Analisis Alimentarios, Lab. de Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain); Simal Lozano, J [Dept. de Quimica Analitica, Nutricion y Bromatologia, Area Nutricion y Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain); Lage Yusty, M A [Inst. de Investigacion y Analisis Alimentarios, Lab. de Bromatologia, Facultad de Farmacia, Santiago de Compostela (Spain)

1996-10-01

A multicomponent extraction/concentration procedure has been developed for the enrichment of PCBs, PCTs and aliphatic hydrocarbons (pristane, C{sub 18}, C{sub 19}, C{sub 20}, C{sub 22}, C{sub 24}, C{sub 28}, C{sub 32} and C{sub 36}) in pork liver. These components of the enriched extract were then simultaneously determined by gas chromatography. Mean recoveries ranged from 81.5% for pristane to 93% for PCBs; CV % (0.9-6.7) indicated the method to be both precise and reproducible. (orig.)

Aliphatic and polycyclic aromatic hydrocarbons characterisation of Coimbra and Oporto PM2.5 urban aerosol

Science.gov (United States)

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

A method for eliminating sulfur compounds from fluid, saturated, aliphatic hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Fakhriev, A.M.; Galiautdinov, N.G.; Kashevarov, L.A.; Mazgarov, A.M.

1982-01-01

The method for eliminating sulfur compounds from fluid, saturated, aliphatic hydrocarbons, which involves extracting hydrocarbons using a dimethylsulfoxide extractant, is improved by using a dimethylsulfoxide blend and 10-60 percent (by volume) diethylenetriamine or polyethylenepolyamine which contains diethylenetriamine, triethylenetetramine and tetraethylenepentamine, in order to eliminate the above compounds. Polyethylenepolyamine is produced as a by-product during the production of ethylenediamine. Elimination is performed at 0-50 degrees and 1-60 atmospheres of pressure. Here, the extractant may contain up to 10 percent water. The use of the proposed method, rather than the existing method, will make it possible to increase hydrocarbon elimination from mercaptans by 40 percent and from H/sub 2/S by 10 percent when the same amount is eliminated from dialkylsulfides.

Design, Synthesis and Cytotoxic Activities of Novel Aliphatic Amino-Substituted Flavonoids

Directory of Open Access Journals (Sweden)

Guannan Liu

2013-11-01

Full Text Available A series of flavonoids 9a–f, 13b, 13d, 13e and 14a–f bearing diverse aliphatic amino moieties were designed, synthesized and evaluated for their cytotoxic activities against the ECA-109, A-549, HL-60, and PC-3 cancer cell lines. Most of the compounds exhibited moderate to good activities. The structure-activity relationships were studied, revealing that the chalcone skeleton is the most preferable for cytotoxic activities. Chalcone 9d was the most promising compound due to its high potency against the examined cancer cell lines (its IC50 values against ECA-109, A549, HL-60 and PC-3 cells were 1.0, 1.5, 0.96 and 3.9 μM, respectively.

Aromatic-aliphatic polyamide/montmorillonite clay nanocomposite materials: Synthesis, nanostructure and properties

International Nuclear Information System (INIS)

Zulfiqar, Sonia; Ahmad, Zahoor; Ishaq, Muhammad; Sarwar, Muhammad Ilyas

2009-01-01

New type of aromatic-aliphatic polyamide/montmorillonite nanocomposites were produced using solution intercalation technique in dimethylacetamide. The modification of clay was carried out with ammonium salt of long chain alkyl amine. The nanocomposites were probed for organoclay dispersion, mechanical, thermal and water absorption measurements. Formation of delaminated and intercalated nanostructures was confirmed by X-ray diffraction and TEM studies. Improvement in tensile strength and modulus was observed for nanocomposites with optimum organoclay content (8-wt.%). Thermogravimetric analysis indicated an increase in thermal stability of nanocomposites as compared to pristine polyamide. Differential scanning calorimetric results revealed increase in glass transition temperatures (T g ) with augmenting organoclay in the nanocomposites. Water uptake of the nanocomposites reduced than the neat polyamide rendering decreased permeability.

Aromatic-aliphatic polyamide/montmorillonite clay nanocomposite materials: Synthesis, nanostructure and properties

Energy Technology Data Exchange (ETDEWEB)

Zulfiqar, Sonia [Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Ahmad, Zahoor [Department of Chemistry, Faculty of Science, Kuwait University, P. O. Box: 5969, Safat 13060 (Kuwait); Ishaq, Muhammad [Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Sarwar, Muhammad Ilyas, E-mail: ilyassarwar@hotmail.com [Department of Chemistry, Quaid-i-Azam University, Islamabad 45320 (Pakistan); Department of Materials Science and Engineering, University of Delaware, Newark, DE 19716 (United States)

2009-11-15

New type of aromatic-aliphatic polyamide/montmorillonite nanocomposites were produced using solution intercalation technique in dimethylacetamide. The modification of clay was carried out with ammonium salt of long chain alkyl amine. The nanocomposites were probed for organoclay dispersion, mechanical, thermal and water absorption measurements. Formation of delaminated and intercalated nanostructures was confirmed by X-ray diffraction and TEM studies. Improvement in tensile strength and modulus was observed for nanocomposites with optimum organoclay content (8-wt.%). Thermogravimetric analysis indicated an increase in thermal stability of nanocomposites as compared to pristine polyamide. Differential scanning calorimetric results revealed increase in glass transition temperatures (T{sub g}) with augmenting organoclay in the nanocomposites. Water uptake of the nanocomposites reduced than the neat polyamide rendering decreased permeability.

Analysis of TPH and Aliphatic and Aromatic Hydrocarbons Fractions in Environmental Interest Matrices

International Nuclear Information System (INIS)

Pindado, O.; Perez, R. M.; Garcia, S.

2014-01-01

Analytical methods to analyze TPH and several aliphatic and aromatic fractions present in soil and groundwater samples contaminated by hydrocarbons are showed. As a part of BIOXISOIL project, analyzing these parameters is fundamental and indispensable to know the initial contamination level, design an adequate method to decontaminate it and eventually assess decontamination accomplished. Analysis of both matrices involve different extraction stages such as microwave radiation, clean up steps based on solid phase extraction and finally a chromatograph analysis with flame ion detector. Analytical procedures have showed satisfactory analytical quality parameters and have been validated against several certified reference materials. (Author)

Synthesis of Novel Aliphatic N-sulfonylamidino Thymine Derivatives by Cu(I)-catalyzed Three-component Coupling Reaction

OpenAIRE

Krstulović, Luka; Ismaili, Hamit; Višnjevac, Aleksandar; Glavaš-Obrovac, Ljubica; Žinić, Biserka

2012-01-01

A series of new aliphatic N-sulfonylamidino thymine derivatives containing nucleobase, N-sulfonyl and amidine pharmacophores in the structure were synthesized by Cu(I)-catalyzed threecomponent coupling of 1-propargyl thymine, benzenesulfonyl azides and amines or ammonium salts. Preliminary in vitro antitumor screening (human cervix adenocarcinoma -HeLa and leukemia cells - Jurkat) revealed promising activities of N,N-diethyl- (2) and N-4-cyanobenzyl- (6) derivatives of 4-acetamido...

Non-Heme Iron Catalysts with a Rigid Bis-Isoindoline Backbone and Their Use in Selective Aliphatic C−H Oxidation

NARCIS (Netherlands)

Chen, Jianming; Lutz, Martin; Milan, Michela; Costas, Miquel; Otte, Matthias; Klein Gebbink, Bert

2017-01-01

Iron complexes derived from a bis-isoindoline-bis-pyridine ligand platform based on the BPBP ligand (BPBP=N,N′-bis(2-picolyl)-2,2′-bis-pyrrolidine) have been synthesized and applied in selective aliphatic C−H oxidation with hydrogen peroxide under mild conditions. The introduction of benzene

Aliphatic and aromatic hydrocarbons in tropical recent sediments of Campos dos Goytacazes, RJ, Brazil

Directory of Open Access Journals (Sweden)

Gomes Alexandre de O.

2003-01-01

Full Text Available Sediment samples from the Imbé, the Urubu and the Ururaí rivers and from Lake de Cima were studied. These sites are located in the county of Campos dos Goytacazes, Rio de Janeiro, Brazil. Aliphatic and aromatic fractions were analyzed by GC-FID and GC-MS in order to gather information on the degree of contamination by anthropogenic activities and other biogenic contributions. Concentrations of total aliphatic and aromatic hydrocarbons were 1.2, 2.8, 5.8 and 4.3 mug g-1 and 74, 30, 722 and 340 ng g-1 in the Imbé, Ururaí, Urubu rivers and Lake de Cima, respectively. The C20 highly branched isoprenoid alkane was identified in the Urubu sediment. There were no hopanes or steranes in any sample. Anthropogenic aromatic compounds, detected at trace levels, were observed only in the Imbé and in Lake de Cima (227 ng g-1. The fluoranthene/pyrene rate for Lake de Cima was 4.2, suggesting a combustion origin for the PAH. This data is consistent with the frequently sugar cane burning practice that occurs in this region. A greater input from higher plants was observed in the Urubu, Imbé and Lake de Cima sediments; on the other hand, the aquatic input predominates for Ururaí. In summary, Lake de Cima sediment is considered very slightly polluted, while the others are unpolluted.

A comprehensive evaluation of the toxicology of cigarette ingredients: aliphatic and aromatic carboxylic acids.

Science.gov (United States)

Coggins, Christopher R E; Liu, Jianmin; Merski, Jerome A; Werley, Michael S; Oldham, Michael J

2011-06-01

Aromatic and aliphatic carboxylic acids are present in tobacco and tobacco smoke. A battery of tests was used to compare the toxicity of mainstream smoke from experimental cigarettes containing eight aromatic and aliphatic carboxylic acids and the salt of one acid that were added individually at three different levels (lowest and highest target inclusions were 100 and 90,000 ppm, respectively). Mainstream smoke from cigarettes containing each of the test ingredients was evaluated using analytical chemistry and assays to measure in vitro cytotoxicity (neutral red uptake) and Salmonella (five strains) mutagenicity. For four of the compounds (citric, lactic, benzoic acids, and sodium benzoate), 90-day rodent inhalation studies were also performed. Although sporadic statistically significant differences in some experimental cigarette smoke constituents occurred, none resulted in significant changes in mutagenicity or cytotoxicity responses, nor in responses measured in the inhalation studies, except for lactic acid (LA). Inclusion of LA resulted in dose-dependent increase in water and caused a dose-dependent decrease in cytotoxicity. Incorporation of LA into cigarettes resulted in several dose-related reductions in histopathology, which were largely restricted to the nasal passages. Incorporation of LA also ameliorated some of the typical decrease in body weight gain seen in cigarette smoke-exposed rats. Inclusion of these ingredients at exaggerated use levels resulted in sporadic dose-related and treatment effects for some smoke constituents, but no toxicological response was noted in the in vitro and in vivo tests performed.

SIMPLE estimate of the free energy change due to aliphatic mutations: superior predictions based on first principles.

Science.gov (United States)

Bueno, Marta; Camacho, Carlos J; Sancho, Javier

2007-09-01

The bioinformatics revolution of the last decade has been instrumental in the development of empirical potentials to quantitatively estimate protein interactions for modeling and design. Although computationally efficient, these potentials hide most of the relevant thermodynamics in 5-to-40 parameters that are fitted against a large experimental database. Here, we revisit this longstanding problem and show that a careful consideration of the change in hydrophobicity, electrostatics, and configurational entropy between the folded and unfolded state of aliphatic point mutations predicts 20-30% less false positives and yields more accurate predictions than any published empirical energy function. This significant improvement is achieved with essentially no free parameters, validating past theoretical and experimental efforts to understand the thermodynamics of protein folding. Our first principle analysis strongly suggests that both the solute-solute van der Waals interactions in the folded state and the electrostatics free energy change of exposed aliphatic mutations are almost completely compensated by similar interactions operating in the unfolded ensemble. Not surprisingly, the problem of properly accounting for the solvent contribution to the free energy of polar and charged group mutations, as well as of mutations that disrupt the protein backbone remains open. 2007 Wiley-Liss, Inc.

EFSA ; Scientific Opinion on Flavouring Group Evaluation 63, Revision 1 (FGE.63Rev1): Consideration of aliphatic secondary alcohols, ketones and related esters evaluated by JECFA (59th and 69th meetings) structurally related to saturated and unsaturated aliphatic secondary alcohols, ketones

DEFF Research Database (Denmark)

Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 19 aliphatic secondary alcohols, ketones and related esters evaluated by the JECFA at the 59th and 69th meetings in 2002 and 2008. This revision is made due to inclusion of six...

Mixed aliphatic and aromatic composition of evaporating very small grains in NGC 7023 revealed by the 3.4/3.3 μm ratio

Science.gov (United States)

Pilleri, P.; Joblin, C.; Boulanger, F.; Onaka, T.

2015-05-01

Context. A chemical scenario was proposed for photon-dominated regions (PDRs) according to which UV photons from nearby stars lead to the evaporation of very small grains (VSGs) and the production of gas-phase polycyclic aromatic hydrocarbons (PAHs). Aims: Our goal is to achieve better insight into the composition and evolution of evaporating very small grains (eVSGs) and PAHs through analyzing the infrared (IR) aliphatic and aromatic emission bands. Methods: We combined spectro-imagery in the near- and mid-IR to study the spatial evolution of the emission bands in the prototypical PDR NGC 7023. We used near-IR spectra obtained with the IRC instrument onboard AKARI to trace the evolution of the 3.3 μm and 3.4 μm bands, which are associated with aromatic and aliphatic C-H bonds on PAHs. The spectral fitting involved an additional broad feature centered at 3.45 μm that is often referred to as the plateau. Mid-IR observations obtained with the IRS instrument onboard the Spitzer Space Telescope were used to distinguish the signatures of eVSGs and neutral and cationic PAHs. We correlated the spatial evolution of all these bands with the intensity of the UV field given in units of the Habing field G0 to explore how their carriers are processed. Results: The intensity of the 3.45 μm plateau shows an excellent correlation with that of the 3.3 μm aromatic band (correlation coefficient R = 0.95) and a relatively poor correlation with the aliphatic 3.4 μm band (R = 0.77). This indicates that the 3.45 μm feature is dominated by the emission from aromatic bonds. We show that the ratio of the 3.4 μm and 3.3 μm band intensity (I3.4/I3.3) decreases by a factor of 4 at the PDR interface from the more UV-shielded layers (G0 ~ 150,I3.4/I3.3 = 0.13) to the more exposed layers (G0> 1 × 104,I3.4/I3.3 = 0.03). The intensity of the 3.3 μm band relative to the total neutral PAH intensity shows an overall increase with G0, associated with an increase of both the hardness of the

The anomalous substituent effect of the ethyl group in the 13 C NMR and IR data of some aliphatic nitriles

International Nuclear Information System (INIS)

Garcia, Janaina C.; Barbarini, Jose E.; Rittner, Roberto; Rocco, Silvana A.; Tormena, Claudio F.

1999-01-01

This work reports a full assignment of 13 C and 1 H chemical shifts for some aliphatic nitriles from acetonitrile to octanonitrile and the observed shieldings for the carbon cyano group are correlated with the ν CN and with the electronic and steric parameters

Development of technology for the alkylation of hydroquinone with aliphatic alcohols

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V. M. Bolotov

2017-01-01

Full Text Available The paper presents the results of research of technology of alkylation of hydroquinone, propyl, isopropyl, isobutyl and tert-butyl alcohols in the presence of concentrated phosphoric acid. The temperature of the alkylation reaction was maintained between 70–72 °С. On the basis of literature data and preliminary investigations the reaction was performed for 4 hours. Upon completion of the reaction, we removed the unreacted hydroquinone, aliphatic alcohol and phosphoric acid are added to a solution of distilled water (solvent corresponding connections and sodium bicarbonate to slightly acidic (pH 5–6. For separation from the reaction medium of alkylhydroquinones in the reaction mixture was added benzene in which the original hydroquinone dissolves much less. Concentration of the benzene extract alkylhydroquinones conducted by Stripping the solvent under vacuum at temperatures above 70 °С in air atmosphere. Higher temperature vacuum distillation AIDS in the oxidation of alkylhydroquinones to alkylphenones. Precipitated after crystallization, alkylhydroquinones were dried under vacuum in a drying pistol at 56 °С. Dried products were identified by defining the melting temperature, the study of spectral characteristics and qualitative reactions with FeCl3. We also studied the solubility of alkylhydroquinones in various solvents, which showed low solubility of alkylhydroquinones in water, benzene, toluene and higher solubility in propyl and isopropyl alcohols and in acetone. Analysis of the results shows that the obtained alkylhydroquinones are not chemically pure compounds, and contain in their composition of admixture source of hydroquinone. Qualitative reactions of solutions of alkylhydroquinones with FeCl3 solution differ from the corresponding reaction of a solution of hydroquinone. The results of investigations of electronic absorption spectra of alkylhydroquinones and source of hydroquinone in isopropyl alcohol solution did not

Organic phosphorus fractionation in wetland soil profiles by chemical extraction and phosphorus-31 nuclear magnetic resonance spectroscopy

International Nuclear Information System (INIS)

Li, Min; Zhang, Jing; Wang, Guangqian; Yang, Haijun; Whelan, Michael J.; White, Sue M.

2013-01-01

Highlights: ► Chemical sequential extraction and 31 P NMR spectroscopy were used for organic P analysis. ► Organic P includes orthophosphate, monoester and diester phosphate and pyrophosphate. ► Highly resistant organic P and monoester phosphate were the dominant organic P. ► HCl pretreatment can remove most inorganic P and increase organic P recovery rate. ► A comprehensive organic P chemical sequential fractionation approach was proposed. - Abstract: Organic P (OP) plays an important role in soil P cycling and is a potential P source for wetland plants. In this study, a modified chemical sequential fractionation method and 31 P nuclear magnetic resonance spectroscopy ( 31 P NMR) of NaOH–EDTA extracts were used to examine the distribution of organic P fractions and compounds in soil profiles of the Beijing Yeyahu Wetland, China. The influence of acid treatment prior to NaOH–EDTA extraction on 31 P NMR spectra was also investigated. Results show that highly resistant OP was the major class of organic P. The rank order of organic P fractions was highly resistant OP (on average accounting for 68.5% of total OP) > moderately resistant OP (15.8%m of total OP) > moderately labile OP (11.4% of total OP) > labile OP (4.3% of total OP). Most of the organic P fractions decreased with soil depth due to the accumulation of plant residues in surface soils and the deposition and diagenesis of soils. Moderately (r = 0.586, p < 0.01) and highly (r = 0.741, p < 0.01) resistant OP fractions were positively correlated with soil organic matter. Phosphorus compounds including orthophosphate (23–74.6% of total P in spectra), monoester phosphate (18.6–76%), diester phosphate (nil-7.8%) and pyrophosphate (nil-6.7%) were characterized using 31 P NMR. Monoester-P was the dominant soil organic P compound identified. The proportion of monoester-P increased significantly in NaOH–EDTA extracts with HCl pretreatment and it was confirmed by chemical analysis. Therefore, it

Mortality of Bemisia tabaci biotype B (sternorrhyncha: aleyrodidae adults by aliphatic and aromatic synthetic sucrose esters

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Mariangela Alves

2008-12-01

Full Text Available The B-strain of Bemisia tabaci Gennadius is a key pest of several crops and chemical control is the main control method used by growers, although reduction in efficacy due to insecticide resistance has already been reported. The aim of this work was to investigate the insecticidal effect of an array of synthetic sucrose esters with the aliphatic and aromatic groups on whitefly adults. Sucrose butyrate, caprate, octanoate, palmitate, oleate, octaacetate, phthalate, benzoate, and sucrose diacetate hexaisobutyrate were tested. The solutions were prepared and applied on the adults caught on yellow sticky traps using the Potter spray tower. Long-chains sucrose aliphatic esters were more effective against the silverleaf whiteflies and the highest mortality was obtained with sucrose oleate and sucrose octanoate. Since these compounds were tensoactive, sodium dodecylsulphate was also tested for the comparison but no effect was observed. Sucrose butyrate and other aliphatic and aromatic sucrose polyesters showed negligible effect on the silverleaf whiteflies.O biótipo B de B. tabaci Gennadius tem se destacado como uma praga-chave de diversas culturas. O controle químico tem sido a principal tática de controle utilizada, embora já se tenha observado redução na eficiência dos produtos devido ao desenvolvimento de resistência. Assim, o objetivo do presente trabalho foi avaliar o efeito de diversos ésteres de sacarose com grupos alifáticos ou aromáticos sobre adultos de mosca-branca. Butirato de sacarose, caprato, octanoato, palmitato, oleato, actaacetato, ftlato, benzoato e diacetato hexaisobutirato de sacarose foram testados. Soluções de éster de sacarose foram preparadas e aplicadas sobre adultos capturados em armadilhas adesivas utilizando Torre de Potter. Ésteres alifáticos de sacarose com longas cadeias foram mais efetivos contra mosca-branca e as maiores taxas de mortalidade foram obtidas com oleato e octanoato de sacarose. Uma vez que

Attachment of inorganic moieties onto aliphatic polyurethanes

Directory of Open Access Journals (Sweden)

Eliane Ayres

2007-06-01

Full Text Available Polyurethanes have been used in a series of applications due basically to their versatility in terms of controlling the behavior by altering basically the type of reagents used. However, for more specific and advanced applications, such as in membranes, biomaterials and sensors, well-organized and defined chemical functionalities are necessary. In this work, inorganic functionalities were incorporated into aliphatic polyurethanes (PU having different macromolecular architectures. Polyurethanes were synthesized using a polyether diol and dicyclohexylmethane 4,4' diisocyanate (H12-MDI. Polyurethanes having carboxylic acid groups were also produced by introducing 2,2- bis (hydroxymethyl propionic acid in the polymerization process. Inorganic functionalities were inserted into polyurethanes by reacting isocyanate end capped chains with aminopropyltriethoxysilane followed by tetraethoxysilane. PU having carboxylic acid groups yielded transparent samples after the incorporation of inorganic entities, as an evidence of smaller and better dispersed inorganic entities in the polymer network. FTIR and swelling measurements showed that polyurethanes having carboxylic acid groups had inorganic domains less packed, condensed and cross-linked when compared to polyurethanes with no carboxylic acid groups. Results also suggested that the progressive incorporation of inorganic moieties in both types of polyurethanes occurred in regions previously activated with inorganic functionalities, instead of by the creation of new domains. The temperatures of thermal decomposition and glass transition were also shifted to higher temperatures when inorganic functionalities were incorporated into polyurethanes.

Quantifying the mechanism of phosphate monoester hydrolysis in aqueous solution by evaluating the relevant ab initio QM/MM free-energy surfaces.

Science.gov (United States)

Plotnikov, Nikolay V; Prasad, B Ram; Chakrabarty, Suman; Chu, Zhen T; Warshel, Arieh

2013-10-24

Understanding the nature of the free-energy surfaces for phosphate hydrolysis is a prerequisite for understanding the corresponding key chemical reactions in biology. Here, the challenge has been to move to careful ab initio QM/MM (QM(ai)/MM) free-energy calculations, where obtaining converging results is very demanding and computationally expensive. This work describes such calculations, focusing on the free-energy surface for the hydrolysis of phosphate monoesters, paying special attention to the comparison between the one water (1W) and two water (2W) paths for the proton-transfer (PT) step. This issue has been explored before by energy minimization with implicit solvent models and by nonsystematic QM/MM energy minimization, as well as by nonsystematic free-energy mapping. However, no study has provided the needed reliable 2D (3D) surfaces that are necessary for reaching concrete conclusions. Here we report a systematic evaluation of the 2D (3D) free-energy maps for several relevant systems, comparing the results of QM(ai)/MM and QM(ai)/implicit solvent surfaces, and provide an advanced description of the relevant energetics. It is found that the 1W path for the hydrolysis of the methyl diphosphate (MDP) trianion is 6-9 kcal/mol higher than that the 2W path. This difference becomes slightly larger in the presence of the Mg(2+) ion because this ion reduces the pKa of the conjugated acid form of the phosphate oxygen that accepts the proton. Interestingly, the BLYP approach (which has been used extensively in some studies) gives a much smaller difference between the 1W and 2W activation barriers. At any rate, it is worth pointing out that the 2W transition state for the PT is not much higher that the common plateau that serves as the starting point of both the 1W and 2W PT paths. Thus, the calculated catalytic effects of proteins based on the 2W PT mechanistic model are not expected to be different from the catalytic effects predicted using the 1W PT mechanistic

Shape memory polymers based on uniform aliphatic urethane networks

Energy Technology Data Exchange (ETDEWEB)

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.

Recent Advances in 3D Printing of Aliphatic Polyesters

Science.gov (United States)

Frone, Adriana Nicoleta; Brandabur, Călin

2017-01-01

3D printing represents a valuable alternative to traditional processing methods, clearly demonstrated by the promising results obtained in the manufacture of various products, such as scaffolds for regenerative medicine, artificial tissues and organs, electronics, components for the automotive industry, art objects and so on. This revolutionary technique showed unique capabilities for fabricating complex structures, with precisely controlled physical characteristics, facile tunable mechanical properties, biological functionality and easily customizable architecture. In this paper, we provide an overview of the main 3D-printing technologies currently employed in the case of poly (lactic acid) (PLA) and polyhydroxyalkanoates (PHA), two of the most important classes of thermoplastic aliphatic polyesters. Moreover, a short presentation of the main 3D-printing methods is briefly discussed. Both PLA and PHA, in the form of filaments or powder, proved to be suitable for the fabrication of artificial tissue or scaffolds for bone regeneration. The processability of PLA and PHB blends and composites fabricated through different 3D-printing techniques, their final characteristics and targeted applications in bioengineering are thoroughly reviewed. PMID:29295559

Recent Advances in 3D Printing of Aliphatic Polyesters

Directory of Open Access Journals (Sweden)

Ioana Chiulan

2017-12-01

Full Text Available 3D printing represents a valuable alternative to traditional processing methods, clearly demonstrated by the promising results obtained in the manufacture of various products, such as scaffolds for regenerative medicine, artificial tissues and organs, electronics, components for the automotive industry, art objects and so on. This revolutionary technique showed unique capabilities for fabricating complex structures, with precisely controlled physical characteristics, facile tunable mechanical properties, biological functionality and easily customizable architecture. In this paper, we provide an overview of the main 3D-printing technologies currently employed in the case of poly (lactic acid (PLA and polyhydroxyalkanoates (PHA, two of the most important classes of thermoplastic aliphatic polyesters. Moreover, a short presentation of the main 3D-printing methods is briefly discussed. Both PLA and PHA, in the form of filaments or powder, proved to be suitable for the fabrication of artificial tissue or scaffolds for bone regeneration. The processability of PLA and PHB blends and composites fabricated through different 3D-printing techniques, their final characteristics and targeted applications in bioengineering are thoroughly reviewed.

Recent Advances in 3D Printing of Aliphatic Polyesters.

Science.gov (United States)

Chiulan, Ioana; Frone, Adriana Nicoleta; Brandabur, Călin; Panaitescu, Denis Mihaela

2017-12-24

3D printing represents a valuable alternative to traditional processing methods, clearly demonstrated by the promising results obtained in the manufacture of various products, such as scaffolds for regenerative medicine, artificial tissues and organs, electronics, components for the automotive industry, art objects and so on. This revolutionary technique showed unique capabilities for fabricating complex structures, with precisely controlled physical characteristics, facile tunable mechanical properties, biological functionality and easily customizable architecture. In this paper, we provide an overview of the main 3D-printing technologies currently employed in the case of poly (lactic acid) (PLA) and polyhydroxyalkanoates (PHA), two of the most important classes of thermoplastic aliphatic polyesters. Moreover, a short presentation of the main 3D-printing methods is briefly discussed. Both PLA and PHA, in the form of filaments or powder, proved to be suitable for the fabrication of artificial tissue or scaffolds for bone regeneration. The processability of PLA and PHB blends and composites fabricated through different 3D-printing techniques, their final characteristics and targeted applications in bioengineering are thoroughly reviewed.

A novel high-performance thin layer chromatography method for quantification of long chain aliphatic hydrocarbons from Cissus quadrangularis

Directory of Open Access Journals (Sweden)

Vandana Jain

2016-08-01

Full Text Available Context: A high-performance thin layer chromatography (HPTLC is an analytical technique, which can be used for the determination of constituents or marker components in various parts of the plants. Earlier studies have estimated phytoconstituents from the stem and other aerial plant parts of Cissus quadrangularis Linn. Estimation of hydrocarbons can also be successfully done using HPTLC technique using suitable derivatization. Aims: To develop and validate a simple and rapid method for the estimation of long chain aliphatic hydrocarbons from the leaves of C. quadrangularis using HPTLC technique. Methods: Precoated silica gel 60 F254 plates were used as stationary phase. The mobile phase used was hexane (100 %. The detection of spots was carried out using berberine sulphate as detecting reagent. Results: The method was validated in terms of linearity, sensitivity, accuracy, and precision. Linearity range was found to be 2-10 µg/mL, limit of detection 0.127 µg/mL, and limit of quantification 0.384 µg/mL. Conclusions: A novel, simple, accurate, precise and sensitive HPTLC method has been developed and validated for the estimation of long chain aliphatic hydrocarbons obtained from the leaves of C. quadrangularis Linn.

Vapour pressures and heat capacity measurements on the C7-C9 secondary aliphatic alcohols

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Schick, Christoph

2007-01-01

Molar enthalpies of vaporization of secondary C 7 -C 9 alkanols were obtained from the temperature dependence of the vapour pressure measured by the transpiration method. The measured data sets were checked for internal consistency successfully. A large number of the primary experimental results on temperature dependences of vapour pressures of secondary alcohols have been collected from the literature and have been treated uniform in order to derive their vaporization enthalpies at the reference temperature 298.15 K. This collection, together with our experimental results, have helped to ascertain the database for branched aliphatic alcohols

Potential of amino acid/dipeptide monoester prodrugs of floxuridine in facilitating enhanced delivery of active drug to interior sites of tumors: a two-tier monolayer in vitro study.

Science.gov (United States)

Tsume, Yasuhiro; Hilfinger, John M; Amidon, Gordon L

2011-10-01

To evaluate the advantages of amino acid/dipeptide monoester prodrugs for cancer treatments by assessing the uptake and cytotoxic effects of floxuridine prodrugs in a secondary cancer cell monolayer following permeation across a primary cancer cell monolayer. The first Capan-2 monolayer was grown on membrane transwell inserts; the second monolayer was grown at the bottom of a plate. The permeation of floxuridine and its prodrugs across the first monolayer and the uptake and cell proliferation assay on secondary layer were sequentially determined. All floxuridine prodrugs exhibited greater permeation across the first Capan-2 monolayer than the parent drug. The correlation between uptake and growth inhibition in the second monolayer with intact prodrug permeating the first monolayer suggests that permeability and enzymatic stability are essential for sustained action of prodrugs in deeper layers of tumors. The correlation of uptake and growth inhibition were vastly superior for dipeptide prodrugs to those obtained with mono amino acid prodrugs. Although a tentative general overall correlation between intact prodrug and uptake or cytotoxic action was obtained, it appears that a mixture of floxuridine prodrugs with varying beneficial characteristics may be more effective in treating tumors.

Functionalization of glassy carbon surface by means of aliphatic and aromatic amino acids. An experimental and theoretical integrated approach

International Nuclear Information System (INIS)

Vanossi, Davide; Benassi, Rois; Parenti, Francesca; Tassinari, Francesco; Giovanardi, Roberto; Florini, Nicola; De Renzi, Valentina; Arnaud, Gaelle; Fontanesi, Claudio

2012-01-01

Highlights: ► Glassy carbon is functionalized via electrochemical assisted grafting of amino acids. ► The grafting mechanism is suggested to involve the “zwitterionic” species. ► DFT calculations allowed to determine the electroactive species. ► An original grafting mechanism is proposed. - Abstract: Glassy carbon (GC) electrode surfaces are functionalized through electrochemical assisted grafting, in oxidation regime, of six amino acids (AA): β-alanine (β-Ala), L-aspartic acid (Asp), 11-aminoundecanoic acid (UA), 4-aminobenzoic acid (PABA), 4-(4-amino-phenyl)-butyric acid (PFB), 3-(4-amino-phenyl)-propionic acid (PFP). Thus, a GC/AA interface is produced featuring carboxylic groups facing the solution. Electrochemical (cyclic voltammetry and electrochemical impedance spectroscopy) and XPS techniques are used to experimentally characterize the grafting process and the surface state. The theoretical results are compared with the experimental evidence to determine, at a molecular level, the overall grafting mechanism. Ionization potentials, standard oxidation potentials, HOMO and electron spin distributions are calculated at the CCD/6-31G* level of the theory. The comparison of experimental and theoretical data suggests that the main electroactive species is the “zwitterionic” form for the three aliphatic amino acids, while the amino acids featuring the amino group bound to the phenyl aromatic moiety show a different behaviour. The comparison between experimental and theoretical results suggests that both the neutral and the zwitterionic forms are present in the acetonitrile solution in the case of 4-(4-amino-phenyl)-butyric acid (PFB) and 3-(4-amino-phenyl)-propionic acid.

Aliphatic polyesters for medical imaging and theranostic applications.

Science.gov (United States)

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. Copyright © 2015 Elsevier B.V. All rights reserved.

Reactivity of polyester aliphatic amine surfactants as corrosion inhibitors for carbon steel in formation water (deep well water)

International Nuclear Information System (INIS)

Alsabagh, A.M.; Migahed, M.A.; Awad, Hayam S.

2006-01-01

Effect of different concentrations, 40-200 ppm, of various polyester aliphatic amine surfactants on inhibition of the corrosion of carbon steel in the formation water (deep well water) was investigated. These surfactants exhibit different levels of inhibition particularly at high concentration (200 ppm). Inhibition efficiencies in the range 86-96% were determined by weight loss method. Comparable results were obtained from electrochemical measurements using Tafel extrapolation and polarisation resistance methods. It was shown that all the investigated surfactants act primarily as anodic inhibitors; however, they also affect the rate and mechanism of the cathodic reaction. These compounds function via adsorption on reactive sites on the corroding surface reducing the corrosion rate of the metal. It was revealed that the adsorption of these surfactants obey Langmuir adsorption isotherm. The inhibition effectiveness increases with the length of the aliphatic hydrocarbon chain, being a maximum in the presence of surfactant IV (∼96% efficiency). The corrosion inhibition feature of this compound is attributed to the presence of a long hydrocarbon chain that ensures large surface coverage as well as the presence of multiple active centers for adsorption. Scanning electron microscopy, SEM, has been applied to identify the surface morphology of carbon steel alloy in the absence and presence of the inhibitor molecules

Reactivity of polyester aliphatic amine surfactants as corrosion inhibitors for carbon steel in formation water (deep well water)

Energy Technology Data Exchange (ETDEWEB)

Alsabagh, A.M. [Department of Petroleum Applications, Egyptian Petroleum Research Institute (EPRI), Ahmed El-Zomor Street 1, Nasr City, Cairo 11727 (Egypt); Migahed, M.A. [Department of Petroleum Applications, Egyptian Petroleum Research Institute (EPRI), Ahmed El-Zomor Street 1, Nasr City, Cairo 11727 (Egypt)]. E-mail: mohamedatiyya707@hotmail.com; Awad, Hayam S. [Chemistry Department, Faculty of Girls for Science, Art and Education, Ain Shams University, Asmaa Fahmi Street, Helliopolis, Cairo (Egypt)

2006-04-15

Effect of different concentrations, 40-200 ppm, of various polyester aliphatic amine surfactants on inhibition of the corrosion of carbon steel in the formation water (deep well water) was investigated. These surfactants exhibit different levels of inhibition particularly at high concentration (200 ppm). Inhibition efficiencies in the range 86-96% were determined by weight loss method. Comparable results were obtained from electrochemical measurements using Tafel extrapolation and polarisation resistance methods. It was shown that all the investigated surfactants act primarily as anodic inhibitors; however, they also affect the rate and mechanism of the cathodic reaction. These compounds function via adsorption on reactive sites on the corroding surface reducing the corrosion rate of the metal. It was revealed that the adsorption of these surfactants obey Langmuir adsorption isotherm. The inhibition effectiveness increases with the length of the aliphatic hydrocarbon chain, being a maximum in the presence of surfactant IV ({approx}96% efficiency). The corrosion inhibition feature of this compound is attributed to the presence of a long hydrocarbon chain that ensures large surface coverage as well as the presence of multiple active centers for adsorption. Scanning electron microscopy, SEM, has been applied to identify the surface morphology of carbon steel alloy in the absence and presence of the inhibitor molecules.

BjuB.CYP79F1 Regulates Synthesis of Propyl Fraction of Aliphatic Glucosinolates in Oilseed Mustard Brassica juncea: Functional Validation through Genetic and Transgenic Approaches.

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Manisha Sharma

Full Text Available Among the different types of methionine-derived aliphatic glucosinolates (GS, sinigrin (2-propenyl, the final product in 3C GS biosynthetic pathway is considered very important as it has many pharmacological and therapeutic properties. In Brassica species, the candidate gene regulating synthesis of 3C GS remains ambiguous. Earlier reports of GSL-PRO, an ortholog of Arabidopsis thaliana gene At1g18500 as a probable candidate gene responsible for 3C GS biosynthesis in B. napus and B. oleracea could not be validated in B. juncea through genetic analysis. In this communication, we report the isolation and characterization of the gene CYP79F1, an ortholog of A. thaliana gene At1g16410 that is involved in the first step of core GS biosynthesis. The gene CYP79F1 in B. juncea showed presence-absence polymorphism between lines Varuna that synthesizes sinigrin and Heera virtually free from sinigrin. Using this presence-absence polymorphism, CYP79F1 was mapped to the previously mapped 3C GS QTL region (J16Gsl4 in the LG B4 of B. juncea. In Heera, the gene was observed to be truncated due to an insertion of a ~4.7 kb TE like element leading to the loss of function of the gene. Functional validation of the gene was carried out through both genetic and transgenic approaches. An F2 population segregating only for the gene CYP79F1 and the sinigrin phenotype showed perfect co-segregation. Finally, genetic transformation of a B. juncea line (QTL-NIL J16Gsl4 having high seed GS but lacking sinigrin with the wild type CYP79F1 showed the synthesis of sinigrin validating the role of CYP79F1 in regulating the synthesis of 3C GS in B. juncea.

A QSPR STUDY OF NORMAL BOILING POINT OF ORGANIC COMPOUNDS (ALIPHATIC ALKANES USING MOLECULAR DESCRIPTORS

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B. Souyei

2013-12-01

Full Text Available A quantitative structure–property relationship (QSPR study is carried out to develop correlations that relate the molecular structures of organic compounds (Aliphatic Alkanes to their normal boiling point (NBP and two correlations were proposed for constitutionals and connectivity indices Models. The correlations are simple in application with good accuracy, which provide an easy, direct and relatively accurate way to calculate NBP. Such calculation gives us a model that gives results in remarkable correlations with the descriptors of blokes constitutionals (CON, and connectivity indices (CI (R2 = 0.950, δ = 0.766 (R2 = 0.969, δ = 0.782 respectively.

Kinetics and mechanism of the selective oxidation of primary aliphatic alcohols under phase transfer catalysis

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K. Bijudas

2014-03-01

Full Text Available Kinetics of the oxidation of primary aliphatic alcohols has been carried out using phase transferred monochromate in benzene. Tetrabutylammonium bromide (TBAB and tetrabutylphosphonium bromide (TBPB are used as phase transfer catalysts (PT catalyst. The reaction shows first order dependence on both [alcohol] and [monochromate ion]. The oxidation leads to the formation of corresponding aldehyde and no traces of carboxylic acid has been detected. The reaction mixture failed to induce the polymerization of added acrylonitrile which rules out the presence radical intermediates in the reaction. Various thermodynamic parameters have been evaluated and a suitable mechanism has been proposed.

The kinetics of reductive dehalogenation of a set of halogenated aliphatic hydrocarbons in anaerobic sediment slurries.

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Peijnenburg, W; Eriksson, L; de Groot, A; Sjöström, M; Verboom, H

1998-01-01

Disappearance rate constants are reported for the reductive transformation of 17 halogenated aliphatic hydrocarbons in anaerobic sediment-water samples. Statistical experimental design in combination with multivariate chemical characterization of their chemical properties was used to select the compounds. Degradation followed pseudo first-order kinetics through at least two half-lives for 15 of the 17 compounds. Of all the compounds investigated, 1,2,3-trichloropropane and dichloromethane were unique in that they were dehalogenated according to zero-order kinetics. Reductive dehalogenation was the sole transformation reaction taking place.

A Hydrazone-Based exo-Directing-Group Strategy for β C-H Oxidation of Aliphatic Amines.

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Huang, Zhongxing; Wang, Chengpeng; Dong, Guangbin

2016-04-18

Described is a new hydrazone-based exo-directing group (DG) strategy developed for the functionalization of unactivated primary β C-H bonds of aliphatic amines. Conveniently synthesized from protected primary amines, the hydrazone DGs are shown to site-selectively promote the β-acetoxylation and tosyloxylation via five-membered exo-palladacycles. Amines with a wide scope of skeletons and functional groups are tolerated. Moreover, the hydrazone DG can be readily removed, and a one-pot C-H acetoxylation/DG removal protocol was also discovered. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Cer-cqu gene cluster determines three key players in a β-diketone synthase polyketide pathway synthesizing aliphatics in epicuticular waxes.

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Schneider, Lizette M; Adamski, Nikolai M; Christensen, Caspar Elo; Stuart, David B; Vautrin, Sonia; Hansson, Mats; Uauy, Cristobal; von Wettstein-Knowles, Penny

2016-03-09

Aliphatic compounds on plant surfaces, called epicuticular waxes, are the first line of defense against pathogens and pests, contribute to reducing water loss and determine other important phenotypes. Aliphatics can form crystals affecting light refraction, resulting in a color change and allowing identification of mutants in their synthesis or transport. The present study discloses three such Eceriferum (cer) genes in barley - Cer-c, Cer-q and Cer-u - known to be tightly linked and functioning in a biochemical pathway forming dominating amounts of β-diketone and hydroxy-β-diketones plus some esterified alkan-2-ols. These aliphatics are present in many Triticeae as well as dicotyledons such as Eucalyptus and Dianthus. Recently developed genomic resources and mapping populations in barley defined these genes to a small region on chromosome arm 2HS. Exploiting Cer-c and -u potential functions pinpointed five candidates, of which three were missing in apparent cer-cqu triple mutants. Sequencing more than 50 independent mutants for each gene confirmed their identification. Cer-c is a chalcone synthase-like polyketide synthase, designated diketone synthase (DKS), Cer-q is a lipase/carboxyl transferase and Cer-u is a P450 enzyme. All were highly expressed in pertinent leaf sheath tissue of wild type. A physical map revealed the order Cer-c, Cer-u, Cer-q with the flanking genes 101kb apart, confirming they are a gene cluster, Cer-cqu. Homology-based modeling suggests that many of the mutant alleles affect overall protein structure or specific active site residues. The rich diversity of identified mutations will facilitate future studies of three key enzymes involved in synthesis of plant apoplast waxes. © The Author 2016. Published by Oxford University Press on behalf of the Society for Experimental Biology.

Distribution of trichloroethylene and selected aliphatic and aromatic hydrocarbons between ''weathered'' and ''unweathered'' fuel mixtures and groundwater: Equilibrium and kinetic considerations

International Nuclear Information System (INIS)

Doucette, W.J.; Dupont, R.R.

1995-01-01

The distribution of trichloroethylene and several aliphatic and aromatic fuel components between 46 weathered and 11 unweathered fuel mixtures and groundwater was investigated using a slow stirring method. The weathered fuel mixtures were obtained from several contaminated field sites. Both unlabeled and 14C-labeled test compounds were used in the distribution experiments. Analyses of the test compound concentrations over time was performed by gas chromatograph or liquid scintillation counting. The time required to reach equilibrium varied from about 24 to 72 hours. Generally, the greater the hydrophobicity of the test compounds the longer time that was required to reach equilibrium. It was also observed that the fuel/water distribution coefficients were generally larger for the weathered fuels than those measured for the unweathered fuels, in some cases by a factor of 100. The weathered fuel mixtures obtained from the field site were depleted of the more water soluble compounds over time and became significantly more enriched in long chain aliphatic hydrocarbons. The ability of several models to describe the observed distribution behavior was examined

The aliphatic hydrocarbon distributions of terrestrial plants around an alpine lake: a pilot study from Lake Ximencuo, Eastern Qinghai-Tibet Plateau

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Pu, Yang; Jia, Jihong; Cao, Jicheng

2017-12-01

As part of an investigation of the sources of aliphatic hydrocarbons to the sediments of alpine Lake Ximencuo, leaves of the eight dominant vascular plants were collected and their hydrocarbon contents were analyzed. A series of unsaturated aliphatic hydrocarbons were identified in the plant leaves; in particular, Festuca sp. contain a series of n-alkadienes that have rarely been reported in previous studies. The comparison of n-alkane proxies (ACL 27-33, ACL T, P aq, and CPI) and δ13Corg among plant leaves, surface soils, and lake sediments suggests that organic proxies have been altered to varying degrees during the transport and burial process of organic materials. It is believed that microbial reworking and source changes have great impacts on organic proxies in the alpine lake system. In addition, the cluster analysis for plant leaves depending on n-alkane compositions and the ACL T proxy generates similar results. Accordingly, we postulate that the average chain length of plant waxes might be a potential indicator of plant classification in regions such as the Qinghai-Tibet Plateau.

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

Science.gov (United States)

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.

Supercritical fluid extraction of triterpenes and aliphatic hydrocarbons from olive tree derivatives

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Aimen Issaoui

2017-05-01

Full Text Available Olive leaves and tree bark were extracted through supercritical fluid extraction (SFE and the chemical composition of the extracted mixture was determined by Gas Chromatography–Mass Spectrometry (GC–MS. Both samples contain a great number of triterpenes as squalene, which were used since 1997 as a main constituent of the flu vaccine (FLUAD, and the alpha-tocopherol the most biologically active form of vitamin E. We also underline the presence of many aliphatic compounds such nonacosane and heptacosane in low concentrations. The extractions were carried out at 313 and 333 K, at a pressure varying from 90 to 250 bars and using pure carbon dioxide in its supercritical phase. Therefore, their solubilities at equilibrium were numerically optimized via two assumptions and compared with the experimental values. Indeed, a good agreement between several results was shown.

Liquid chromatographic separation and indirect detection of non-absorbing aliphatic compounds using m-nitrophenol as a detection agent

International Nuclear Information System (INIS)

Lee, Seung Seok; Kang, Sam Woo; Moon, Young Ja

1991-01-01

m-Nitrophenol(m-NP) was a detection agent for the use of the detection and separation of non-absorbing compounds such as aliphatic acids, alcohols, amines and tetraalkylammonium salts by indirect photometric detection in reversed-phase liquid chromatography. Response of samples was investigated to the several factors such as pH, temperature, and concentration of MeOH as well as concentration of detection reagent in mobile phase. The separation of several mixtures were attempted under optimum condition. (Author)

Synthesis and characterization of soluble, blue-fluorescent polyamides and polyimides containing substituted p-terphenyl as well as long aliphatic segments in the main chain

NARCIS (Netherlands)

Mikroyannidis, JA; Tsivgoulis, GM

1999-01-01

A novel class of semiflexible polyamides and polyimides bearing substituted p-terphenyl as well as long aliphatic segments in the main chain were synthesized through pyrylium salts. Characterization of polymers was accomplished by inherent viscosity, elemental analysis, FT-IR, NMR, UV-vis

Abilities of some higher plants to hydrolyze the acetates of phenols and aromatic-aliphatic alcohols

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Agnieszka Mironowicz

2014-01-01

Full Text Available In the biotransformations carried out under the same conditions, the whole intact plants of Spirodela punctata, Nephrolepis exaltata, Cyrtomium falcatum, Nephrolepis cordifolia and the suspension cultures of Helianthus tuberosus, Daucus carota and Petunia hybrida hydrolyze (partially or totally the ester bonds of the acetates of phenols and aromatic-aliphatic alcohols and also the menthyl acetate. Nevertheless, the methyl esters of aromatic acids, structurally similar to the former substrates, do not undergo hydrolysis. At the same time, the viability of first four plants was observed for different levels of acetate concentration. The method of continuous preparative hydrolysis of the same acetates was worked out in Cyrtomium falcatum culture.

Increased mean aliphatic lipid chain length in left ventricular hypertrophy secondary to arterial hypertension: A cross-sectional study.

Science.gov (United States)

Evaristi, Maria Francesca; Caubère, Céline; Harmancey, Romain; Desmoulin, Franck; Peacock, William Frank; Berry, Matthieu; Turkieh, Annie; Barutaut, Manon; Galinier, Michel; Dambrin, Camille; Polidori, Carlo; Miceli, Cristina; Chamontin, Bernard; Koukoui, François; Roncalli, Jerôme; Massabuau, Pierre; Smih, Fatima; Rouet, Philippe

2016-11-01

About 77.9 million (1 in 4) American adults have high blood pressure. High blood pressure is the primary cause of left ventricular hypertrophy (LVH), which represents a strong predictor of future heart failure and cardiovascular mortality. Previous studies have shown an altered metabolic profile in hypertensive patients with LVH. The goal of this study was to identify blood metabolomic LVH biomarkers by H NMR to provide novel diagnostic tools for rapid LVH detection in populations of hypertensive individuals. This cross-sectional study included 48 hypertensive patients with LVH matched with 48 hypertensive patients with normal LV size, and 24 healthy controls. Two-dimensional targeted M-mode echocardiography was performed to measure left ventricular mass index. Partial least squares discriminant analysis was used for the multivariate analysis of the H NMR spectral data. From the H NMR-based metabolomic profiling, signals coming from methylene (-CH2-) and methyl (-CH3) moieties of aliphatic chains from plasma lipids were identified as discriminant variables. The -CH2-/-CH3 ratio, an indicator of the mean length of the aliphatic lipid chains, was significantly higher (P hypertensive group without LVH and controls. Receiver operating characteristic curve showed that a cutoff of 2.34 provided a 52.08% sensitivity and 85.42% specificity for discriminating LVH (AUC = 0.703, P-value hypertension.

Hydrocarbons (aliphatic and aromatic) in the snow-ice cover in the Arctic

International Nuclear Information System (INIS)

Nemirovskaya, I.A.; Novigatsky, A.N.; Kluvitkin, A.A.

2002-01-01

This paper presented the concentration and composition of aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) in snow and ice-infested waters in the France-Victoria trough in the northern Barents Sea and in the Mendeleev ridge in the Amerasian basin of the Arctic Ocean. Extreme conditions such as low temperatures, ice sheets and the polar nights render the arctic environment susceptible to oil spills. Hydrocarbons found in these northern seas experience significant transformations. In order to determine the sources, pathways and transformations of the pollutants, it is necessary to know their origin. Hydrocarbon distributions is determined mostly by natural hydrobiological and geochemical conditions. The regularity of migration is determined by natural factors such as formation and circulation of air and ice drift. There is evidence suggesting that the hydrocarbons come from pyrogenic sources. It was noted that hydrocarbons could be degraded even at low temperatures. 17 refs., 1 tab

Ru (III) Catalyzed Oxidation of Aliphatic Ketones by N-Bromosuccinimide in Aqueous Acetic Acid: A Kinetic Study

Science.gov (United States)

Giridhar Reddy, P.; Ramesh, K.; Shylaja, S.; Rajanna, K. C.; Kandlikar, S.

2012-01-01

Kinetics of Ru (III) catalyzed oxidation of aliphatic ketones such as acetone, ethyl methyl ketone, diethyl ketone, iso-butylmethyl ketone by N-bromosuccinimide in the presence of Hg(II) acetate have been studied in aqueous acid medium. The order of [N-bromosuccinimide] was found to be zero both in catalyzed as well as uncatalyzed reactions. However, the order of [ketone] changed from unity to a fractional one in the presence of Ru (III). On the basis of kinetic features, the probable mechanisms are discussed and individual rate parameters evaluated. PMID:22654610

Environmentally friendly chemoselective oxidation of primary aliphatic amines by using a biomimetic electrocatalytic system.

Science.gov (United States)

Largeron, Martine; Chiaroni, Angèle; Fleury, Maurice-Bernard

2008-01-01

Environmentally friendly oxidation of primary aliphatic amines to imines has been successfully achieved, under metal-free conditions, by the use of diverse electrogenerated o-azaquinone mediators. High catalytic performance, together with high chemoselectivity, were observed with electron-poor o-azaquinone catalysts generated from 2-aminoresorcinol derivatives. Similar to copper amine oxidase enzymes, these mediators exhibited lower reactivity toward alpha-branched primary amines and no reactivity toward secondary amines. In the case of 3,4-aminophenol derivatives lacking a 2-hydroxy group, the generated o-azaquinone species failed to catalyze the oxidation of the amine to the corresponding imine. Further mechanistic considerations allowed a rationalization of the crucial role of the 2-hydroxy group in converting a catalytically inert species into a highly effective biomimetic catalyst.

Study of the electron beam irradiation effect on some properties of aromatic aliphatic copolyester films

International Nuclear Information System (INIS)

Poveda, Patricia Negrini Siqueira

2008-01-01

Biodegradable and green plastics are the new tendency in the world. The effect of the electron beam irradiation in aromatic aliphatic copolyester and the blend with corn starch films (Ecoflex R and Ecobras R ) were studied by tensile strength at break, elongation at break, Scanning Electronic Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), Differential Scanning Calorimetry (DSC), crosslinking degree and biodegradability. The measurements in both, the machine direction and the transverse direction were made for mechanical tests. It was found that, the electron irradiation caused an increase in the strength at break of the blend with corn starch film, when doses of up to 10 kGy were applied. A significant decrease of the elongation at break of the blend with corn starch was observed at doses of 10 kGy and 40 kGy. It was not found important change in tensile properties for aromatic aliphatic copolyester. Structural changes of the samples (crosslinking or degradation) by SEM were not observed. The FT-IR identified the characteristic peaks of each involved functional group (copolyester and corn starch). However, it was not found bands of oxidation of the samples. In the DSC, changes in the melting temperature of the irradiated Ecoflex R and Ecobras R samples, was not identified when compared with the samples of reference. However, it was verified a reduction in the melting enthalpy of the Ecobras R samples after irradiation. The Ecobras R material presented crosslinking, when submitted to doses of 10 kGy and 40 kGy. The Ecoflex R material did not present crosslinking when submitted to these doses. The biodegradability of the materials was evaluated by two methods of test: soil simulated and enzymatic. In both methods, the irradiated samples presented faster biodegradation than the references not irradiated. (author)

Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

Science.gov (United States)

Malloy, Q. G. J.; Qi, Li; Warren, B.; Cocker, D. R., III; Erupe, M. E.; Silva, P. J.

2009-03-01

Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine) are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (tested) as detected by an aerosol mass spectrometer (AMS). We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

Secondary organic aerosol formation from primary aliphatic amines with NO3 radical

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P. J. Silva

2009-03-01

Full Text Available Primary aliphatic amines are an important class of nitrogen containing compounds emitted from automobiles, waste treatment facilities and agricultural animal operations. A series of experiments conducted at the UC-Riverside/CE-CERT Environmental Chamber is presented in which oxidation of methylamine, ethylamine, propylamine, and butylamine with O3 and NO3 have been investigated. Very little aerosol formation is observed in the presence of O3 only. However, after addition of NO, and by extension NO3, large aerosol mass yields (~44% for butylamine are seen. Aerosol generated was determined to be organic in nature due to the small fraction of NO and NO2 in the total signal (<1% for all amines tested as detected by an aerosol mass spectrometer (AMS. We propose a reaction mechanism between carbonyl containing species and the parent amine leading to formation of particulate imine products. These findings can have significant impacts on rural communities with elevated nighttime PM loadings, when significant levels of NO3 exist.

Escherichia coli as a potential hydrocarbon conversion microorganism. Oxidation of aliphatic and aromatic compounds by recombinant E. coli in two-liquid phase (aqueous-organic) systems

NARCIS (Netherlands)

Favre-Bulle, Olivier

1992-01-01

The increased interest in the study of hydrocarbon utilizing microorganisms in recent years has been stimulated by the possibility of using their monooxygenases in the selective oxidation of aliphatic and aromatic compounds. As an example, long chain (>C16) n-alkanes are converted to dicarboxylic

UPLC-ESI-MS/MS method for the quantitative measurement of aliphatic diamines, trimethylamine N-oxide, and β-methylamino-l-alanine in human urine.

Science.gov (United States)

Bhandari, Deepak; Bowman, Brett A; Patel, Anish B; Chambers, David M; De Jesús, Víctor R; Blount, Benjamin C

2018-04-15

This work describes a quantitative high-throughput analytical method for the simultaneous measurement of small aliphatic nitrogenous biomarkers, i.e., 1,6-hexamethylenediamine (HDA), isophoronediamine (IPDA), β-methylamino-l-alanine (BMAA), and trimethylamine N-oxide (TMAO), in human urine. Urinary aliphatic diamines, HDA and IPDA, are potential biomarkers of environmental exposure to their corresponding diisocyanates. Urinary BMAA forms as a result of human exposure to blue-green algae contaminated food. And, TMAO is excreted in urine due to the consumption of carnitine- and choline-rich diets. These urinary biomarkers represent classes of small aliphatic nitrogen-containing compounds (N-compounds) that have a high aqueous solubility, low logP, and/or high basic pK a . Because of the highly polar characteristics, analysis of these compounds in complex sample matrices is often challenging. We report on the development of ion-pairing chemistry based ultra-performance liquid chromatography-electrospray ionization-tandem mass spectrometry (UPLC-ESI-MS/MS) method for the simultaneous measurement of these biomarkers in human urine. Chromatographic separation was optimized using heptafluorobutyric acid-(HFBA-) based mobile phase and a reversed-phase C18 column. All four analytes were baseline separated within 2.6 min with an overall run time of 5 min per sample injection. Sample preparation involved 4 h of acid hydrolysis followed by automated solid phase extraction (SPE) performed using strong cation exchange sorbent bed with 7 N ammonia solution in methanol as eluent. Limits of detection ranged from 0.05 ng/mL to 1.60 ng/mL. The inter-day and intra-day accuracy were within 10%, and reproducibility within 15%. The method is accurate, fast, and well-suited for biomonitoring studies within targeted groups, as well as larger population-based studies such as the U. S. National Health and Nutrition Examination Survey (NHANES). Published by Elsevier B.V.

Selective hydrolysis of phosphate monoester by a supramolecular phosphatase formed by the self-assembly of a bis(Zn(2+)-cyclen) complex, cyanuric acid, and copper in an aqueous solution (cyclen = 1,4,7,10-tetraazacyclododecane).

Science.gov (United States)

Zulkefeli, Mohd; Suzuki, Asami; Shiro, Motoo; Hisamatsu, Yosuke; Kimura, Eiichi; Aoki, Shin

2011-10-17

In Nature, organized nanoscale structures such as proteins and enzymes are formed in aqueous media via intermolecular interactions between multicomponents. Supramolecular and self-assembling strategies provide versatile methods for the construction of artificial chemical architectures for controlling reaction rates and the specificities of chemical reactions, but most are designed in hydrophobic environments. The preparation of artificial catalysts that have potential in aqueous media mimicking natural enzymes such as hydrolases remains a great challenge in the fields of supramolecular chemistry. Herein, we describe that a dimeric Zn(2+) complex having a 2,2'-bipyridyl linker, cyanuric acid, and a Cu(2+) ion automatically assembles in an aqueous solution to form a 4:4:4 complex, which is stabilized by metal-ligand coordination bonds, π-π-stacking interactions, and hydrogen bonding and contains μ-Cu(2)(OH)(2) cores analogous to the catalytic centers of phosphatase, a dinuclear metalloenzyme. The 4:4:4 complex selectively accelerates the hydrolysis of a phosphate monoester, mono(4-nitrophenyl)phosphate, at neutral pH.

Platinum-Catalyzed Terminal-Selective C(sp3)–H Oxidation of Aliphatic Amines

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S.

2016-01-01

This paper describes the terminal-selective Pt-catalyzed C(sp3)–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 (ii) it electronically deactivates the C–H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp3)–H oxidation of a variety of primary, secondary and tertiary amines. PMID:26439251

Carbon-rich dust past the asymptotic giant branch: Aliphatics, aromatics, and fullerenes in the Magellanic Clouds

Energy Technology Data Exchange (ETDEWEB)

Sloan, G. C.; Lagadec, E. [Center for Radiophysics and Space Research, Cornell University, Ithaca, NY 14853-6801 (United States); Zijlstra, A. A. [Jodrell Bank Centre for Astrophysics, University of Manchester, Manchester M13 9PL (United Kingdom); Kraemer, K. E. [Institute for Scientific Research, Boston College, 140 Commonwealth Avenue, Chestnut Hill, MA 02467 (United States); Weis, A. P. [Department of Astronomy and Astrophysics, Columbia University, 550 West 120th Street, New York, NY 10027 (United States); Matsuura, M. [Astrophysics Group, Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom); Volk, K. [Space Telescope Science Institute, 3700 San Martin Drive, Baltimore, MD 21218 (United States); Peeters, E.; Cami, J. [Department of Physics and Astronomy, University of Western Ontario, London, ON N6A 3K7 (Canada); Duley, W. W. [Department of Physics and Astronomy, University of Waterloo, 200 University Avenue West, Waterloo, ON N2L 3G1 (Canada); Bernard-Salas, J. [Department of Physical Sciences, The Open University, Walton Hall, Milton Keynes, MK7 6AA (United Kingdom); Kemper, F. [Academia Sinica, Institute of Astronomy and Astrophysics, 11F Astronomy-Mathematics Building, NTU/AS, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan, R.O.C (China); Sahai, R., E-mail: sloan@isc.astro.cornell.edu [Jet Propulsion Laboratory, MS 183-900, California Institute of Technology, Pasadena, CA 91109 (United States)

2014-08-10

Infrared spectra of carbon-rich objects that have evolved off the asymptotic giant branch reveal a range of dust properties, including fullerenes, polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons, and several unidentified features, including the 21 μm emission feature. To test for the presence of fullerenes, we used the position and width of the feature at 18.7-18.9 μm and examined other features at 17.4 and 6-9 μm. This method adds three new fullerene sources to the known sample, but it also calls into question three previous identifications. We confirm that the strong 11 μm features seen in some sources arise primarily from SiC, which may exist as a coating around carbonaceous cores and result from photo-processing. Spectra showing the 21 μm feature usually show the newly defined Class D PAH profile at 7-9 μm. These spectra exhibit unusual PAH profiles at 11-14 μm, with weak contributions at 12.7 μm, which we define as Class D1, or show features shifted to ∼11.4, 12.4, and 13.2 μm, which we define as Class D2. Alkyne hydrocarbons match the 15.8 μm feature associated with 21 μm emission. Sources showing fullerene emission but no PAHs have blue colors in the optical, suggesting a clear line of sight to the central source. Spectra with 21 μm features and Class D2 PAH emission also show photometric evidence for a relatively clear line of sight to the central source. The multiple associations of the 21 μm feature with aliphatic hydrocarbons suggest that the carrier is related to this material in some way.

Carbon-rich dust past the asymptotic giant branch: Aliphatics, aromatics, and fullerenes in the Magellanic Clouds

International Nuclear Information System (INIS)

Sloan, G. C.; Lagadec, E.; Zijlstra, A. A.; Kraemer, K. E.; Weis, A. P.; Matsuura, M.; Volk, K.; Peeters, E.; Cami, J.; Duley, W. W.; Bernard-Salas, J.; Kemper, F.; Sahai, R.

2014-01-01

Infrared spectra of carbon-rich objects that have evolved off the asymptotic giant branch reveal a range of dust properties, including fullerenes, polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons, and several unidentified features, including the 21 μm emission feature. To test for the presence of fullerenes, we used the position and width of the feature at 18.7-18.9 μm and examined other features at 17.4 and 6-9 μm. This method adds three new fullerene sources to the known sample, but it also calls into question three previous identifications. We confirm that the strong 11 μm features seen in some sources arise primarily from SiC, which may exist as a coating around carbonaceous cores and result from photo-processing. Spectra showing the 21 μm feature usually show the newly defined Class D PAH profile at 7-9 μm. These spectra exhibit unusual PAH profiles at 11-14 μm, with weak contributions at 12.7 μm, which we define as Class D1, or show features shifted to ∼11.4, 12.4, and 13.2 μm, which we define as Class D2. Alkyne hydrocarbons match the 15.8 μm feature associated with 21 μm emission. Sources showing fullerene emission but no PAHs have blue colors in the optical, suggesting a clear line of sight to the central source. Spectra with 21 μm features and Class D2 PAH emission also show photometric evidence for a relatively clear line of sight to the central source. The multiple associations of the 21 μm feature with aliphatic hydrocarbons suggest that the carrier is related to this material in some way.

Chemical composition of pseudo-phlobaphinite precursors: implications for the presence of aliphatic biopolymers in vitrinite from coal

Energy Technology Data Exchange (ETDEWEB)

Etuan Zhang; Hatcher, P.G.; Davis, A. (Pennsylvania State University, University Park, PA (United States). Dept. of Materials Science and Engineering)

1993-08-01

Pseudo-phlobaphinite cell inclusions in a buried stem of angiospermous wood of [ital Rhizophora mangle] from Mangrove Lake, Bermuda have been investigated petrographically and chemically. Optical and scanning electron microscopy reveal that the light wood from inner sections of the stem consists predominantly of cell walls with few cell inclusions, whereas the dark wood from outer portion of the stem is composed of both cell walls and cell inclusions which are believed to represent pseudophlobaphinite precursors. [sup 13]C NMR spectroscopy reveals the presence of lignin and tannin structures within the cell walls. The wood also displays resonances suggestive of aliphatic components. The NMR results are further supplemented and confirmed by flash pyrolysis gas chromatography and mass spectrometry analyses. The pyrogram of the cell-wall dominated light wood is characterized by peaks related to both syringyl and guaiacyl units. The major pyrolysis products from the dark wood, however, are a homologous series of long-chain n-alkanes, n-alk-l-enes and [alpha],[omega]-alkadienes extending from chain length C[sub 10] to C[sub 30]. These aliphatic components arise from the material associated with the pseudophlobaphinite cell inclusions. Py-gc/ms analysis of a humic acid extracted from the sediments surrounding the studied wood consists almost exclusively of a homologous series of straight-chain alkanes, alkenes and alkadienes up to C[sub 30]. The striking resemblance between programs of the pseudo-phlobaphinite precursor and humic acid suggests that the possible mechanism for the formation of the pseudo-phlobaphinite is migration and deposition of humic acid into cell lumina. 72 refs., 5 figs., 1 tab.

Morphology and thermal properties of PLA films plasticized with aliphatic oligoesters

International Nuclear Information System (INIS)

Inacio, Erika M.; Dias, Marcos L.; Lima, Maria Celiana P.

2015-01-01

The addition of plasticizers to poly(lactic acid) (PLA) is one of the known ways of changing its ductility, making possible the modification of its mechanical and thermal properties. In this work, it was synthesized two biodegradable aliphatic oligoesters: oligo(trimethylene sebacate) (OST) and oligo(trimethylene malonate) (OMT), and these oligomers were used as plasticizer in cast films of commercial film grade PLA at concentrations of 1, 5 and 10 wt% of each plasticizer. X-ray diffraction (XRD) was used to investigate the morphology and differential scanning calorimetry (DSC) was also used aiming the evaluation of the thermal properties of these films. The PLA films containing no plasticizer showed an amorphous behavior, and the addition of PMT on the PLA films acted, simultaneously, decreasing the Tg, and rising the material's crystallinity. In contrast, the increased addition of OST to the PLA films did not change the Tg, and equally, did not have a significant changes in the material's crystallinity. Therefore, it was possible to observe the effect of the concentration of oligomers on the crystallinity of the films as well as the no plasticizer effect of the OST. (author)

Physico-chemical properties of binary mixtures of aliphatic and aromatic solvents at 313 K on acoustical data

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Dahire, S. L.; Morey, Y. C.; Agrawal, P. S.

2015-12-01

Density (ρ), viscosity (η), and ultrasonic velocity ( U) of binary mixtures of aliphatic solvents like dimethylformamide (DMF) and dimethylsulfoxide (DMSO) with aromatic solvents viz. chlorobenzene (CB), bromobenzene (BB), and nitrobenzene (NB) have been determined at 313 K. These parameters were used to calculate the adiabatic compressibility (β), intermolecular free length ( L f), molar volume ( V m), and acoustic impedance ( Z). From the experimental data excess molar volume ( V m E ), excess intermolecular free length ( L f E )), excess adiabatic compressibility (βE), and excess acoustic impedance ( Z E) have been computed. The excess values were correlated using Redlich-Kister polynomial equation to obtain their coefficients and standard deviations (σ).

Selective fluorescence quenching of nitrogen-containing polycyclic aromatic hydrocarbons by aliphatic amines

International Nuclear Information System (INIS)

Li Xiaoping; McGuffin, Victoria L.

2004-01-01

In this investigation, primary, secondary, and tertiary amines are evaluated for their efficiency and selectivity as fluorescence quenchers for polycyclic aromatic hydrocarbons (PAHs) and nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). In general, the quenching efficiency tends to increase from primary to tertiary amine due to a greater number of alkyl groups that increase the electron-donating ability. However, the selectivity decreases from primary to tertiary amine. The effect of low concentrations of water is also examined. Because water can form hydrogen bonds with amines, the nonbonding electron pair is not available for interaction with the fluorophore, thus the quenching constant is decreased. These aliphatic amines are then applied to PAHs and N-PAHs and some interesting trends are observed. Whereas amino-PAHs remain virtually unquenched by different amines, aza-PAHs are all quenched well. The selectivity between aza-PAHs and amino-PAHs is as high as several hundred. This trend provides an easy and effective method to discriminate between these classes of N-PAHs. Moreover, the alternant aza-PAHs are quenched more than their corresponding alternant PAHs

Acid-base thermochemistry of gaseous aliphatic α-aminoacids.

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Bouchoux, Guy; Huang, Sihua; Inda, Bhawani Singh

2011-01-14

Acid-base thermochemistry of isolated aliphatic amino acids (denoted AAA): glycine, alanine, valine, leucine, isoleucine and proline has been examined theoretically by quantum chemical computations at the G3MP2B3 level. Conformational analysis on neutral, protonated and deprotonated species has been used to identify the lowest energy conformers and to estimate the population of conformers expected to be present at thermal equilibrium at 298 K. Comparison of the G3MP2B3 theoretical proton affinities, PA, and ΔH(acid) with experimental results is shown to be correct if experimental thermochemistry is re-evaluated and adapted to the most recent acidity-basicity scales. From this point of view, a set of evaluated proton affinities of 887, 902, 915, 916, 919 and 941 kJ mol(-1), and a set of evaluated ΔH(acid) of 1433, 1430, 1423, 1423, 1422 and 1426 kJ mol(-1), is proposed for glycine, alanine, valine, leucine, isoleucine and proline, respectively. Correlations with structural parameters (Taft's σ(α) polarizability parameter and molecular size) suggest that polarizability of the side chain is the major origin of the increase in PA and decrease in ΔH(acid) along the homologous series glycine, alanine, valine and leucine/isoleucine. Heats of formation of gaseous species AAA, AAAH(+) and [AAA-H](-) were computed at the G3MP2B3 level. The present study provides previously unavailable Δ(f)H°(298) for the ionized species AAAH(+) and [AAA-H](-). Comparison with Benson's estimate, and correlation with molecular size, show that several experimental Δ(f)H°(298) values of neutral or gaseous AAA might be erroneous.

Seasonal variation of aliphatic amines in marine sub-micrometer particles at the Cape Verde islands

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H. Herrmann

2009-12-01

Full Text Available Monomethylamine (MA, dimethylamine (DMA and diethylamine (DEA were detected at non-negligible concentrations in sub-micrometer particles at the Cap Verde Atmospheric Observatory (CVAO located on the island of São Vicente in Cape Verde during algal blooms in 2007. The concentrations of these amines in five stage impactor samples ranged from 0–30 pg m⁻³ for MA, 130–360 pg m⁻³ for DMA and 5–110 pg m⁻³ for DEA during the spring bloom in May 2007 and 2–520 pg m⁻³ for MA, 100–1400 pg m⁻³ for DMA and 90–760 pg m⁻³ for DEA during an unexpected winter algal bloom in December 2007. Anomalously high Saharan dust deposition and intensive ocean layer deepening were found at the Atmospheric Observatory and the associated Ocean Observatory during algal bloom periods. The highest amine concentrations in fine particles (impactor stage 2, 0.14–0.42 μm indicate that amines are likely taken up from the gas phase into the acidic sub-micrometer particles. The contribution of amines to the organic carbon (OC content ranged from 0.2–2.5% C in the winter months, indicating the importance of this class of compounds to the carbon cycle in the marine environment. Furthermore, aliphatic amines originating from marine biological sources likely contribute significantly to the nitrogen content in the marine atmosphere. The average contribution of the amines to the detected nitrogen species in sub-micrometer particles can be non-negligible, especially in the winter months (0.1% N–1.5% N in the sum of nitrate, ammonium and amines. This indicates that these smaller aliphatic amines can be important for the carbon and the nitrogen cycles in the remote marine environment.

Gas-Phase Reactions of Dimethyl Disulfide with Aliphatic Carbanions - A Mass Spectrometry and Computational Study

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Franczuk, Barbara; Danikiewicz, Witold

2018-03-01

Ion-molecule reactions of Me2S2 with a wide range of aliphatic carbanions differing by structure and proton affinity values have been studied in the gas phase using mass spectrometry techniques and DFT calculations. The analysis of the spectra shows a variety of product ions formed via different reaction mechanisms, depending on the structure and proton affinity of the carbanion. Product ions of thiophilic reaction ( m/z 47), SN2 ( m/z 79), and E2 elimination - addition sequence of reactions ( m/z 93) can be observed. Primary products of thiophilic reaction can undergo subsequent SN2 and proton transfer reactions. Gibbs free energy profiles calculated for experimentally observed reactions using PBE0/6-311+G(2d,p) method show good agreement with experimental results. [Figure not available: see fulltext.

Potentiometric studies on ternary complexes involving some divalent transition metal ions, gallic acid and biologically abundant aliphatic dicarboxylic acids in aqueous solutions

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Abdelatty Mohamed Radalla

2015-06-01

Full Text Available Formation of binary and ternary complexes of the divalent transition metal ions, Cu2+, Ni2+, Co2+ and Zn2+ with gallic acid and the biologically important aliphatic dicarboxylic acids (adipic, succinic, malic, malonic, maleic, tartaric and oxalic acids were investigated by means of the potentiometric technique at 25 °C and I = 0.10 mol dm−3 NaNO3. The acid-base properties of the ligands were investigated and discussed. The acidity constants of gallic acid and aliphatic dicarboxylic acids were determined and used for determining the stability constants of the binary and ternary complexes formed in the aqueous medium under the above experimental conditions. The formation of the different 1:1 and 1:2 binary complexes and 1:1:1 ternary complexes are inferred from the corresponding potentiometric pH-metric titration curves. The ternary complex formation was found to occur in a stepwise manner. The stability constants of these binary and ternary systems were calculated. The values of Δ log K, percentage of relative stabilization (%R.S. and log X were evaluated and discussed. The concentration distribution of the various complex species formed in solution was evaluated and discussed. The mode of chelation of ternary complexes formed was ascertained by conductivity measurements.

Avocado fruit maturation and ripening: dynamics of aliphatic acetogenins and lipidomic profiles from mesocarp, idioblasts and seed.

Science.gov (United States)

Rodríguez-López, Carlos Eduardo; Hernández-Brenes, Carmen; Treviño, Víctor; Díaz de la Garza, Rocío I

2017-09-29

Avocado fruit contains aliphatic acetogenins (oft-acetylated, odd-chain fatty alcohols) with promising bioactivities for both medical and food industries. However, we have scarce knowledge about their metabolism. The present work aimed to study changes in acetogenin profiles from mesocarp, lipid-containing idioblasts, and seeds from 'Hass' cultivar during fruit development, germination, and three harvesting years. An untargeted LC-MS based lipidomic analysis was also conducted to profile the lipidome of avocado fruit in each tissue. The targeted analysis showed that acetogenin profiles and contents remained unchanged in avocado mesocarp during maturation and postharvest ripening, germination, and different harvesting years. However, a shift in the acetogenin profile distribution, accompanied with a sharp increase in concentration, was observed in seed during early maturation. Untargeted lipidomics showed that this shift was accompanied with remodeling of glycerolipids: TAGs and DAGs decreased during fruit growing in seed. Remarkably, the majority of the lipidome in mature seed was composed by acetogenins; we suggest that this tissue is able to synthesize them independently from mesocarp. On the other hand, lipid-containing idioblasts accumulated almost the entire acetogenin pool measured in the whole mesocarp, while only having 4% of the total fatty acids. The lipidome of this cell type changed the most when the fruit was ripening after harvesting, TAGs decreased while odd-chain DAGs increased. Notably, idioblast lipidome was more diverse than that from mesocarp. Evidence shown here suggests that idioblasts are the main site of acetogenin biosynthesis in avocado mesocarp. This work unveiled the prevalence of aliphatic acetogenins in the avocado fruit lipidome and evidenced TAGs as initial donors of the acetogenin backbones in its biosynthesis. It also sets evidence for acetogenins being included in future works aimed at characterizing the avocado seed, as they are

Boiling points of halogenated aliphatic compounds: a quantitative structure-property relationship for prediction and validation.

Science.gov (United States)

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.

A simple and selective method for determination of phthalate biomarkers in vegetable samples by high pressure liquid chromatography-electrospray ionization-tandem mass spectrometry.

Science.gov (United States)

Zhou, Xi; Cui, Kunyan; Zeng, Feng; Li, Shoucong; Zeng, Zunxiang

2016-06-01

In the present study, solid-phase extraction cartridges including silica reversed-phase Isolute C18, polymeric reversed-phase Oasis HLB and mixed-mode anion-exchange Oasis MAX, and liquid-liquid extractions with ethyl acetate, n-hexane, dichloromethane and its mixtures were compared for clean-up of phthalate monoesters from vegetable samples. Best recoveries and minimised matrix effects were achieved using ethyl acetate/n-hexane liquid-liquid extraction for these target compounds. A simple and selective method, based on sample preparation by ultrasonic extraction and liquid-liquid extraction clean-up, for the determination of phthalate monoesters in vegetable samples by liquid chromatography/electrospray ionisation-tandem mass spectrometry was developed. The method detection limits for phthalate monoesters ranged from 0.013 to 0.120 ng g(-1). Good linearity (r(2)>0.991) between MQLs and 1000× MQLs was achieved. The intra- and inter-day relative standard deviation values were less than 11.8%. The method was successfully used to determine phthalate monoester metabolites in the vegetable samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of large volume injection of aliphatic alcohols as sample diluents on the retention of low hydrophobic solutes in reversed-phase liquid chromatography.

Science.gov (United States)

David, Victor; Galaon, Toma; Aboul-Enein, Hassan Y

2014-01-03

Recent studies showed that injection of large volume of hydrophobic solvents used as sample diluents could be applied in reversed-phase liquid chromatography (RP-LC). This study reports a systematic research focused on the influence of a series of aliphatic alcohols (from methanol to 1-octanol) on the retention process in RP-LC, when large volumes of sample are injected on the column. Several model analytes with low hydrophobic character were studied by RP-LC process, for mobile phases containing methanol or acetonitrile as organic modifiers in different proportions with aqueous component. It was found that starting with 1-butanol, the aliphatic alcohols can be used as sample solvents and they can be injected in high volumes, but they may influence the retention factor and peak shape of the dissolved solutes. The dependence of the retention factor of the studied analytes on the injection volume of these alcohols is linear, with a decrease of its value as the sample volume is increased. The retention process in case of injecting up to 200μL of upper alcohols is dependent also on the content of the organic modifier (methanol or acetonitrile) in mobile phase. Copyright © 2013 Elsevier B.V. All rights reserved.

New regioselective multicomponent reaction: one pot synthesis of spiro heterobicyclic aliphatic rings.

Science.gov (United States)

Byk, G; Gottlieb, H E; Herscovici, J; Mirkin, F

2000-01-01

In the context of our high-throughput organic synthesis program, we have studied the reactivity of special beta-keto esters toward the Biginelli reaction. We have found that a cyclic beta-keto ester reacts with one molecule of urea and two molecules of aldehyde to give a new family of spiro heterobicyclic aliphatic rings in good yields. Interestingly, the Biginelli product was not detected. After analysis of products using HPLC, 1H NMR, and 13C NMR, we have found that the reaction is driven by a regio-specific condensation of two molecules of aldehyde with the other reagents to afford only products harboring substituents exclusively in cis configuration. Monte Carlo minimization studies using MM2 force field suggest that cis products are energetically more stable than the trans counterparts. Together with previously reported data, these results suggest that the trans products were not obtained as result of steric hindrance produced by the equatorial position of one of the ring substituents. This new reaction is useful for high-throughput organic synthesis. Indeed, the new scaffold can be used to introduce additional groups in the molecules through remaining functional groups by a "domino strategy".

Synthesis of Carbon Nanotubes of Few Walls Using Aliphatic Alcohols as a Carbon Source

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Francisco Espinosa-Magaña

2013-06-01

Full Text Available Carbon nanotubes with single and few walls are highly appreciated for their technological applications, regardless of the limited availability due to their high production cost. In this paper we present an alternative process that can lead to lowering the manufacturing cost of CNTs of only few walls by means of the use of the spray pyrolysis technique. For this purpose, ferrocene is utilized as a catalyst and aliphatic alcohols (methanol, ethanol, propanol or butanol as the carbon source. The characterization of CNTs was performed by scanning electron microscopy (SEM and transmission electron microscopy (TEM. The study of the synthesized carbon nanotubes (CNTs show important differences in the number of layers that constitute the nanotubes, the diameter length, the quantity and the quality as a function of the number of carbons employed in the alcohol. The main interest of this study is to give the basis of an efficient synthesis process to produce CNTs of few walls for applications where small diameter is required.

The use of DNA technologies in determining the biotreatability of chlorinated aliphatic hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Douglas, A. [HydroQual, Calgary, AB (Canada)

2008-07-01

HydroQual Laboratories is a wholly-owned subsidiary of Golder Associates and uses biological testing for measuring the effect of toxins and their impact on various links in the food chain in order to evaluate and improve environmental health. It has expertise in various fields of the natural sciences and is ISO certified. This presentation discussed the use of DNA technologies in determining the biotreatability of chlorinated aliphatic hydrocarbons. The paper presented biotreatability studies run by the company which included bench scale testing on various types of contaminants. The testing involved multiple treatments, determination of dosage, and additional amendments. The strategy may vary based on bench test results and legislation. Trichloroethylene/perchloroethylene remediation strategies were also presented for chemical oxidation; aerobic bioremediation; abiotic remediation; and anaerobic biostimulation and augmentation. Biostimulation was defined as the addition of nutrients to influence the redox potential. The presentation also reviewed anaerobic dehalorespiration; detection methods; DNA isolation; polymerase chain reaction (PCR); and biotreatability case studies. The presentation concluded with some future directions and other uses of PCR. tabs., figs.

Partial molar volumes of organic solutes in water. XXVII. Two aliphatic polyethers (triglyme, tetraglyme) at temperatures T = 298–573 K and pressures up to 30 MPa

International Nuclear Information System (INIS)

Cibulka, Ivan

2016-01-01

Highlights: • Standard molar volumes of two linear aliphatic polyethers in water are presented. • Data were obtained in the range T from (298 to 573) K and p up to 30 MPa. • Data combined with those obtained previously are analyzed and compared with standard molar volumes of cyclic ethers. - Abstract: Densities of dilute aqueous solutions of two linear aliphatic polyethers: 2,5,8,11-tetraoxadodecane (triethylene glycol dimethyl ether, triglyme) and 2,5,8,11,14-pentaoxapentadecane (tetraethylene glycol dimethyl ether, tetraglyme), measured in the temperature range from (298 to 573) K and at pressures up to 30 MPa using an automated flow vibrating-tube densimeter are reported. Standard molar volumes were evaluated from the measured data. The present values complement previous measurements performed for the title polyethers at atmospheric pressure in the temperature range from (278 to 343) K and extend the knowledge to temperature and pressure ranges in which the data on standard molar volumes for lower members of the homologous series (monoglyme, diglyme) are already available.

Non-coding RNA/microRNA-modulatory dietary factors and natural products for improved cancer therapy and prevention: Alkaloids, organosulfur compounds, aliphatic carboxylic acids and water-soluble vitamins

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Bernhard Biersack

2016-10-01

Full Text Available Non-coding small RNA molecules, the microRNAs (miRNAs, contribute decisively to the epigenetic regulation processes in cancer cells. Problematic pathogenic properties of cancer cells and the response of cancers towards anticancer drugs are highly influenced by miRNAs. Both increased drug activity and formation of tumor resistance are regulated by miRNAs. Further to this, the survival and proliferation of cancer cells and the formation of metastases is based on the modulated expression of certain miRNAs. In particular, drug-resistant cancer stem-like cells (CSCs depend on the presence and absence of specific miRNAs. Fortunately, several small molecule natural compounds were discovered that target miRNAs involved in the modulation of tumor aggressiveness and drug resistance. This review gives an overview of the effects of a selection of naturally occurring small molecules (alkaloids, organosulfur compounds, aliphatic carboxylic acids and water-soluble vitamins on miRNAs that are closely tangled with cancer diseases. Keywords: MiRNA, Alkaloids, Organosulfur compounds, Aliphatic carboxylic acids, Water-soluble vitamins, Anticancer drugs

Synthesis of α-MoO3 nanoplates using organic aliphatic acids and investigation of sunlight enhanced photodegradation of organic dyes

International Nuclear Information System (INIS)

Kumar, V. Vinod; Gayathri, K.; Anthony, Savarimuthu Philip

2016-01-01

Graphical abstract: Thermodynamically stable α-MoO 3 nanoplates and nanorods were synthesized using organic structure controlling agents and demonstrated sun light enhanced photocatalytic degradation of methylene blue (MB) and rhodamine blue (Rh-B) dyes in aqueous solution. - Highlights: • α-MoO 3 hexagonal nanoplates using organic structure controlling agents. • Tunable optical band gap of MoO 3 . • Demonstrated strong sun light mediated enhanced photodegradation of methylene blue and rhodamine blue. • Photodegradation did not use any other external oxidizing agents. - Abstract: Thermodynamically stable α-MoO 3 nanoplates were synthesized using organic aliphatic acids as structure controlling agents and investigated photocatalytic degradation of methylene blue (MB) and rhodamine blue (Rh-B) in presence of sun light. Three different organic aliphatic acids, citric acid (CA), tartaric acid (TA) and ethylene diamine tetra-acetic acid (EDTA), were employed to control morphologies. CA and TA predominantly produced extended hexagonal plates where EDTA gave nanorods as well as nanoplates. PXRD studies confirmed the formation of α-MoO 3 nanoparticles. HR-TEM and FE-SEM reveal the formation of plate morphologies with 20–40 nm thickness, 50–100 nm diameter and 600 nm lengths. The different morphologies of α-MoO 3 nanoparticles lead to the tunable optical band gap between 2.80 and 2.98 eV which was obtained from diffused reflectance spectra (DRS). Interestingly, the synthesized α-MoO 3 nanoplates exhibited strong photocatalytic degradation of MB and Rh-B up to 99% in presence of sun light without using any oxidizing agents.

Development of four-component synthesis of tetra- and pentasubstituted polyfunctional dihydropyrroles: free permutation and combination of aromatic and aliphatic amines.

Science.gov (United States)

Lv, Longyun; Zheng, Sichao; Cai, Xiaotie; Chen, Zhipeng; Zhu, Qiuhua; Liu, Shuwen

2013-04-08

We previously reported the novel efficient proton/heat-promoted four-component reactions (4CRs) of but-2-ynedioates, two same/different primary amines, and aldehydes for the synthesis of tetra- and pentasubstituted polyfunctional dihydropyrroles. If aromatic and aliphatic amines were used as reagents, four different series of products should be obtained via the permutation and combination of aromatic and aliphatic primary amines. However, only three/two rather four different series of tetra-/pentasubstisuted dihydropyrroles could be prepared via the proton/heat-promoted 4CRs. Herein, Cu(OAc)2·H2O, a Lewis acid being stable in air and water, was found to be an efficient catalyst for the 4CR synthesis of all the four different series of tetra-/pentasubstisuted dihydropyrroles. The copper-catalyzed 4CR could produce target products at room temperature in good to excellent yields. Interestingly, benzaldehyde, in addition to being used as a useful reactant for the synthesis of pentasubstituted dihydropyrroles, was found to be an excellent additive for preventing the oxidation of aromatic amines with copper(II) and ensuring the sooth conduct of the 4CRs for the synthesis of tetrasubstituted dihydropyrroles with aryl R(3). In addition, salicylic acid was found to be needed to increase the activities and yields of the copper-catalyzed 4CRs for the synthesis of petasubstituted diyhydropyrroles. On the basis of experimental results, the enamination/amidation/intramolecular cyclization mechanism was proposed and amidation is expected to be the rate-limited step in the copper-catalyzed 4CRs.

Substituent effects on the photolysis of methyl 2-carboxylate substituted aliphatic 2 H-azirines

Science.gov (United States)

Gómez-Zavaglia, Andrea; Kaczor, Agnieszka; Cardoso, Ana L.; Pinho e Melo, Teresa M. V. D.; Fausto, Rui

2007-05-01

In this study, the UV induced photochemical reactions of two 2 H-azirines - methyl 2-chloro-3-methyl-2 H-azirine-2-carboxylate (MCMAC) and methyl 3-methyl-2 H-azirine-2-carboxylate (MMAC) - isolated in argon matrices are compared. For both compounds, irradiation with λ > 235 nm led to observation of two primary photoprocesses: (a) C sbnd C bond cleavage, with production of nitrile ylides (P1-type products), and (b) C sbnd N bond cleavage, with production of methylated ketene imines (P2-type products). However, subsequent photoprocesses were found to be different in the two cases. In MCMAC, both primary photoproducts were shown to undergo further reactions: P1-type products decarboxylate, giving [(1-chloroethylidene)imino]ethanide, which bears a C dbnd N +dbnd C - group (P3-type product); P2-type products decarbonylate, yielding a substituted ylidene methanamine (P4-type product). In MMAC, only P2-type primary photoproducts appeared to react, undergoing decarbonylation or decarboxylation (both reactions leading to P4-type products), whereas P1-type products were found to be non-reactive. The non-observation of any secondary photoproduct resulting from photolysis of P1-MMAC revealed the higher photostability of this species when compared with the corresponding photoproduct obtained from MCMAC. The C sbnd N photochemical cleavage is an unusual process in aliphatic 2 H-azirines. In the studied compounds, its preference over the commonly observed C sbnd C azirine-ring bond photocleavage is attributed to the presence of electron withdrawing substituents (methylcarboxy group in both azirines and also the chlorine atom in MCMAC), which accelerates intersystem crossing towards the triplet state from where the cleavage of the C sbnd N bond takes place. The lack of the chlorine atom in MMAC may be partially compensated by the significantly higher stabilization of the P2-type photoproduct derived from this molecule ( ca. -52 kJ mol -1) relatively to the reactant, when

Anomalous regioselective four-member multicomponent Biginelli reaction II: one-pot parallel synthesis of spiro heterobicyclic aliphatic rings.

Science.gov (United States)

Byk, Gerardo; Kabha, Eihab

2004-01-01

In a previous preliminary study, we found that a cyclic five-member ring beta-keto ester (lactone) reacts with one molecule of urea and two of aldehyde to give a new family of spiro heterobicyclic aliphatic rings in good yields with no traces of the expected dihydropyrimidine (Biginelli) products. The reaction is driven by a regiospecific condensation of two molecules of aldehyde with urea and beta-keto-gamma-lactone to afford only products harboring substitutions exclusively in a syn configuration (Byk, G.; Gottlieb, H. E.; Herscovici, J.; Mirkin, F. J. Comb. Chem. 2000, 2, 732-735). In the present work ((a) Presented in part at ISCT Combitech, October 15, 2002, Israel, and Eurocombi-2, Copenhagen 2003 (oral and poster presentation). (b) Also in American Peptide Society Symposium, Boston, 2003 (poster presentation). (c) Abstract in Biopolymers 2003, 71 (3), 354-355), we report a large and exciting extension of this new reaction utilizing parallel organic synthesis arrays, as demonstrated by the use of chiral beta-keto-gamma-lactams, derived from natural amino acids, instead of tetronic acid (beta-keto-gamma-lactone) and the potential of the spirobicyclic products for generating "libraries from libraries". Interestingly, we note an unusual and important anisotropy effect induced by perpendicular interactions between rigid pi systems and different groups placed at the alpha position of the obtained spirobicyclic system. Stereo/regioselectivity of the aldehyde condensation is driven by the nature of the substitutions on the starting beta-keto-gamma-lactam. Aromatic aldehydes can be used as starting reagents with good yields; however, when aliphatic aldehydes are used, the desired products are obtained in poor yields, as observed in the classical Biginelli reaction. The possible reasons for these poor yields are addressed and clarify, to some extent, the complexity of the Biginelli multicomponent reaction mechanism and, in particular, the mechanism of the present

Comparison of decomposition characteristics between aromatic and aliphatic VOCs using electron beam

International Nuclear Information System (INIS)

Kim, Jo-Chun

2011-01-01

The removal efficiency of n-decane (C 10 H 22 ) by electron beam was the highest among aliphatic VOCs of concern, and that of n-hexane (C 6 H 14 ), n-butane (C 4 H 10 ), and methane (CH 4 ) followed. On the other hand, in terms of aromatic VOC decomposition efficiencies, benzene (C 6 H 6 ) decomposition was the lowest and that of toluene (C 7 H 8 ), ethylbenzene (C 8 H 10 ), and p-xylene (C 8 H 10 ) were similar. It was also found that there was increase in by-product (untreated VOC, CO, CO 2 , O 3 , and other compounds) formation as well as all VOC removal efficiencies. It was demonstrated that the removal efficiency of VOC increased as its concentration decreased and the irradiation dose increased. In addition, low removal efficiency was observed because helium was relatively stable compared to the other gases, and nothing but electrons produced by electron accelerator reacted with VOC. It was also found that relative humidity had some effects on the decomposition rates of VOC. The removal efficiency at the 100% RH condition was slightly higher than that at 7.4% RH (dry condition) due to OH radical formation. (author)

Aliphatic alcohol contaminants of illegally produced spirits inhibit phagocytosis by human granulocytes.

Science.gov (United States)

Pál, László; Árnyas, Ervin M; Tóth, Béla; Ádám, Balázs; Rácz, Gábor; Ádány, Róza; McKee, Martin; Szűcs, Sándor

2013-04-01

Unregulated production of spirits in many countries leads to products containing appreciable levels of aliphatic alcohols (AAs) and is the main source of human exposure to these substances worldwide. Previous studies have confirmed that alcohol abuse can lead to ethanol-induced immunosuppression and thereby increased susceptibility to infectious diseases. Granulocytes, as professional phagocytic cells, play a crucial role in engulfment and killing of pathogenic microorganisms. Thus, a decrease in their phagocytic activity has been invoked as a factor in the impaired antimicrobial defense observed in alcoholics. However, AAs consumed as contaminants of illicit spirits may also influence phagocytosis, thereby contributing to a further decrease in microbicidal activity but, so far, this has not been studied. Therefore, the aim of this study was to measure granulocyte phagocytosis following treatment of granulocytes with those higher alcohols found in illegal spirits. Granulocytes were isolated from human peripheral blood. Then phagocytosis of opsonized zymosan particles by granulocytes treated with AAs individually and in combination was determined. These alcohols inhibited phagocytosis in a concentration-dependent manner and at lower concentrations when combined than when tested individually. Due to their synergistic effects, it is possible that, in combination with ethanol, they may inhibit phagocytosis in a clinically meaningful way in episodic heavy drinkers.

Aliphatic semisynthetic amino terminal variants of myoglobin: enrichment with carbon-13, determination and interpretation of terminal pK values and motions

International Nuclear Information System (INIS)

Busch, M.R.

1985-01-01

The synthesis of a series of myoglobins substituted in the amino terminal residue to provide variation in the aliphatic nature of the side chain and enrichment in 13 C was accomplished by semisynthetic methods. The replacements of valine, the native first residue, included 13 C enriched glycine, alanine, valine, leucine, and isoleucine. The products were extensively characterized and found to be virtually indistinguishable by most physical methods. 13 C NMR spectroscopy showed significant differences in the amino terminal pK value, ranging from 7.72 for myoglobin to 7.15 for myoglobin. Consideration of the electrostatic effects of the charge array indicated a balance of interactions at this site not significantly altered by variations in the side chain. By examination of the crystal structure, consideration of earlier work regarding the interactions of the side chain of Leu-2, and data regarding the motions of the terminal residue, it was concluded that the interaction of the side chain of the first residue with the hydrophobic cluster formed primarily by close contact of invariant residues Leu-2 and Leu-137 was the primary cause for the reduction in the terminal pK values seen for the larger aliphatics. By restricting the freedom of the residue, this interaction limits the available hydration volume, and consequently favors the unprotonated form of the amine. The concurrent observation of both functional elements in the series of α amino terminal residues brings out the interrelated consequences for the two categories of solvent interactions controlling structural and functional properties in a graded way

Distribution of aliphatic hydrocarbons, polycyclic aromatic hydrocarbons and organochlorinated pollutants in deep-sea sediments of the Southern Cretan margin, Eastern Mediterranean Sea: a baseline assessment.

Science.gov (United States)

Mandalakis, Manolis; Polymenakou, Paraskevi N; Tselepides, Anastasios; Lampadariou, Nikolaos

2014-07-01

Deep sediments from the southern Cretan margin were analyzed to establish baseline levels for various types of organic pollutants before the anticipated intensification of anthropogenic activities. The total concentration of aliphatic hydrocarbons (ΣAH:326-3758ngg(-1), dry weight) was similar to those reported for deep sediments of the western Mediterranean Sea, while considerably lower levels were measured for polycyclic aromatic hydrocarbons (ΣPAH:9-60ngg(-1)). Source-diagnostic ratios suggested that the aliphatic hydrocarbons in sediments were mainly of terrestrial biogenic origin, while polycyclic aromatic hydrocarbons stemmed from the deposition of long-range transported combustion aerosols. Among the organochlorinated compounds analyzed, β-hexachlorocyclohexane (β-HCH:222-7052pgg(-1)), 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (p,p'-DDT:37-2236pgg(-1)) and polychlorinated biphenyls (ΣPCB:38-1182pgg(-1)) showed the highest abundance in sediments. The presence of HCHs and PCBs was attributed to historical inputs that have undergone extensive weathering, whereas an ongoing fresh input was suggested for p,p'-DDT. Multiple linear regression analysis revealed that the levels of the various pollutants in sediments were controlled by different factors, but with organic carbon content playing a prominent role in most cases. Copyright © 2014 Elsevier Ltd. All rights reserved.

Gold recovery from acidic leach solutions using as extractants trialkylamines of N,N'-di-alkyl-aliphatic amides

Energy Technology Data Exchange (ETDEWEB)

Baroncelli, F.; Carlini, D.; Gasparini, G.M.; Simonetti, E.

1988-07-01

TriOctylAmine (TOA) and a di-substituted aliphatic amide, N,N-Di-N-ButylOctanamide (DBOA), were examined in batch and in mini mixer-settler experiments using leachates of Peruvian and Bolivian concentrates. With these minerals, very rich in sulfur (pyrites, stybine), 90-95% gold recovery in 12-24 hours was reached by leaching with 4M aqua regia (HCl 3M nitric acid 1M) at room temperature and with 1/3 solid/liquid ratio. With these leachate solutions (2-3M total acidity, 10-60 ppm ao Au), the two processes with TOA (GAMEX PROCESS) and with DBOA (AUMIDEX PROCESS) were tested and compared. Experimental results strongly support the possibility of using TOA and DBOA on an industrial scale.

Enzymatic monoesterification of symmetric diols: restriction of molecular conformations influences selectivity.

Science.gov (United States)

Tomer, Sanjiv O; Soni, Hemant P

2017-10-31

We have experimentally demonstrated that by 'locking' the molecular conformation through the introduction of a double or triple bond in the center of a symmetric diol, enzymatic monoesterification can be achieved selectively. The enzyme Candida antarctica lipase B, generally used for the transesterification of diols, can be effectively used for the monoesterification of symmetrical diols in an unbuffered system also. By varying the chain length of a carboxylic acid moiety, we have established that optimum selectivity and efficiency can be achieved in the range of 4.8 to 5.0 pK a values. Selectivity can be improved up to 98.75% for a monoester in an overall 73% yield (mixture of a monoester and a diester) when but-2-yne-1,4-diol reacted with hexanoic acid. Water, a by-product, provides an interfacial environment for the enzyme to work in the organic reaction medium. The uniqueness of the reported monoesterification protocol is that it involves only the mechanical stirring of the reaction mixture at room temperature in the presence of the enzyme for 24 h. High percentage yield with selectivity for a monoester, easier product isolation and overall, environmental sustainability are added advantages. The synthesized monoesters are characterized by using HNMR and high resolution mass spectrometry (HRMS).

Comparison of decomposition characteristics between aromatic and aliphatic VOCs using electron beam

Energy Technology Data Exchange (ETDEWEB)

Kim, Jo-Chun [Department of Environmental Engineering, Konkuk University, Seoul (Korea, Republic of)

2011-07-01

The removal efficiency of n-decane (C{sub 10}H{sub 22}) by electron beam was the highest among aliphatic VOCs of concern, and that of n-hexane (C{sub 6}H{sub 14}), n-butane (C{sub 4}H{sub 10}), and methane (CH{sub 4}) followed. On the other hand, in terms of aromatic VOC decomposition efficiencies, benzene (C{sub 6}H{sub 6}) decomposition was the lowest and that of toluene (C{sub 7}H{sub 8}), ethylbenzene (C{sub 8}H{sub 10}), and p-xylene (C{sub 8}H{sub 10}) were similar. It was also found that there was increase in by-product (untreated VOC, CO, CO{sub 2}, O{sub 3}, and other compounds) formation as well as all VOC removal efficiencies. It was demonstrated that the removal efficiency of VOC increased as its concentration decreased and the irradiation dose increased. In addition, low removal efficiency was observed because helium was relatively stable compared to the other gases, and nothing but electrons produced by electron accelerator reacted with VOC. It was also found that relative humidity had some effects on the decomposition rates of VOC. The removal efficiency at the 100% RH condition was slightly higher than that at 7.4% RH (dry condition) due to OH radical formation. (author)

Influence of Phthalates on in vitro Innate and Adaptive Immune Responses

DEFF Research Database (Denmark)

Hansen, Juliana Frohnert; Nielsen, Claus Henrik; Brorson, Marianne Møller

2015-01-01

Phthalates are a group of endocrine disrupting chemicals, suspected to influence the immune system. The aim of this study was to investigate the influence of phthalates on cytokine secretion from human peripheral blood mononuclear cells. Escherichia coli lipopolysaccharide and phytohemagglutinin......-P were used for stimulation of monocytes/macrophages and T cells, respectively. Cells were exposed for 20 to 22 hours to either di-ethyl, di-n-butyl or mono-n-butyl phthalate at two different concentrations. Both diesters were metabolised to their respective monoester and influenced cytokine secretion......-α and interferon-γ by T cells. The investigated phthalate monoester also influenced cytokine secretion from monocytes/macrophages similar to that of the diesters. In T cells, however, the effect of the monoester was different compared to the diesters. The influence of the phthalates on the cytokine secretion did...

THE EFFECT OF SULPHURIC ACID CONCENTRATION ON SOLVENT EXTRACTION OF ReO4 - BY THE LONG-CHAIN ALIPHATIC TERTIARY AMINES AND ALCOHOLS

Directory of Open Access Journals (Sweden)

Aleksander G. Kasikov

2010-06-01

Full Text Available The effect of sulphuric acid concentration on solvent extraction of ReO4- by the long-chain aliphatic tertiary amines and alcohols in a wide range of H2SO4 concentrations in initial solutions is discussed. It has been established that the influence of the sulphuric acid concentration on rhenium solvent extraction is largely due to the extraction process mechanism. In the case of the anion-exchange mechanism, ReO4- is best extracted from weakly acidic solutions, whereas when the hydrate-solvate mechanism takes place – from solutions containing 4-7 mole/l H2SO4.

Kinetics of the reactions of bromine atoms with a series of aliphatic aldehydes at 298 K

Energy Technology Data Exchange (ETDEWEB)

Szilagyi, I.; Imrik, K.; Dobe, S.; Berces, T. [Magyar Tudomanyos Akademia, Budapest (Hungary). Koezponti Kemiai Kutato Intezete

1998-01-01

The kinetics of the reactions of Br({sup 2}P{sub 3/2}) with selected aldehydes, i.e. ethanal (1), propanal (2), 2-methyl-propanal (3), 2.2-dimethyl-propanal (4) and trichloroacetaldehyde (5) were studied at 298{+-}2 K. Rate constants for overall reactions were measured using the fast flow technique with resonance fluorescence detection of Br. Complementary determinations were carried out by the laser flash photolysis method. The following rate constants were obtained in the kinetic measurements ({+-}2{sigma}): k{sub 1}=(2.1{+-}0.2) x 10{sup 12}, k{sub 2}=(4.3{+-}0.4) x 10{sup 12}, k{sub 3}=(6.3{+-}1.4) x 10{sup 12}, k{sub 4}=(8.5{+-}0.8) x 10{sup 12}, k{sub 5}{<=}1 x 10{sup 9}, all in cm{sup 3}mol{sup -1}s{sup -1} units. The probable mechanism for the reactions of bromine atoms with aliphatic aldehydes has been discussed. (orig.)

Mathematical simulation of the kinetics of radiation induced hydroxyalkylation of aliphatic saturated alcohols

International Nuclear Information System (INIS)

Silaev, M.M.; Bugaenko, L.T.

1992-01-01

The paper reports on the development of the kinetics of radiation hydroxymethylation and hydroxypropylation chain processes relating to aliphatic saturated alcohols in the γ-radiolysis of the alcohol-unsaturated compound systems to give 1,2- and 1,4-diols respectively. These processes were simulated mathematically. The kinetic curves computed are in good agreement with the experimental dependences. The kinetic parameters of the processes, including the rate constants for the addition of α-hydroxyalkyl radicals from the saturated alcohols to the double bond of the unsaturated component, viz formaldehyde or 2-propene-1-ol in the systems, were estimated. The constants (in dm 3 /mol.s) for the saturated alcohol-formaldehyde systems incorporating ethanol as the saturated alcohol were found to be (1.5±0.3).10 4 at 413 K and (2.1±0.5).10 4 at 443K; incorporating 1-propanol- (6.0±1.3).10 3 at 413 K; for the saturated alcohol-2-propene-1-ol systems incorporating methanol, ethanol, 1- and 2-propanol-(2.5±0.3).10 4 , (6.5±0.9).10 4 , (2.7±0.4).10 4 and (1.0±0.1).10 5 , respectively, at 433 K. (author)

Swift heavy ion induced modification of aliphatic polymers

International Nuclear Information System (INIS)

Hossain, Umme Habiba

2015-01-01

In this thesis, the high energy heavy ion induced modification of aliphatic polymers is studied. Two polymer groups, namely polyvinyl polymers (PVF, PVAc, PVA and PMMA) and fluoropolymers (PVDF, ETFE, PFA and FEP) were used in this work. Polyvinyl polymers were investigated since they will be used as insulating materials in the superconducting magnets of the new ion accelerators of the planned International Facility for Antiproton and Ion Research (FAIR) at the GSI Helmholtz-Centre of Heavy Ion Research (GSI) in Darmstadt. In order to study ion-beam induced degradation, all polymer foils were irradiated at the GSI linear accelerator UNILAC using several projectiles (U, Au, Sm, Xe) and experimentation sites (beam lines X0 and M3) over a large fluence regime (1 x 10 10 - 5 x 10 12 ions/cm 2 ). Five independent techniques, namely infrared (FT-IR) and ultraviolet-visible (UV-Vis) spectroscopy, residual gas analysis (RGA), thermal gravimetric analysis (TGA), and mass loss analysis (ML), were used to analyze the irradiated samples. FT-IR spectroscopy revealed that ion irradiation led to the decrease of characteristic band intensities showing the general degradation of the polymers, with scission of side groups and the main backbone. As a consequence of the structural modification, new bands appeared. UV-Vis transmission analysis showed an absorption edge shift from the ultraviolet region towards the visible region indicating double bond and conjugated double bond formation. On-line massspectrometric residual gas analysis showed the release of small gaseous fragment molecules. TGA analysis gave evidence of a changed thermal stability. With ML analysis, the considerable mass loss was quantified. The results of the five complementary analytical methods show how heavy ion irradiation changes the molecular structure of the polymers. Molecular degradation mechanisms are postulated. The amount of radiation damage is found to be sensitive to the used type of ionic species. While

Aliphatic hydrocarbon and polycyclic aromatic hydrocarbon geochemistry of twelve major rivers in the Northwest Territories

International Nuclear Information System (INIS)

Backus, S.; Swyripa, M.; Peddle, J.; Jeffries, D.S.

1995-01-01

Suspended sediment and water samples collected from twelve major rivers in the Northwest Territories were analyzed for aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) to assess the sources and transport of hydrocarbons entering the Arctic Ocean. Three stations on the Mackenzie River and one station near the mouth of eleven other northern rivers were selected for sampling. Samples were collected on the Mackenzie River on four occasions to characterize spring, summer and fall flow conditions and once on the remaining eleven rivers during high flow conditions. The Mackenzie River is distinctively different then the other eleven rivers. Naturally occurring hydrocarbons predominate in the river. These hydrocarbons include biogenic alkanes, diagenic PAHs, petrogenic alkanes, and PAHs from oil seeps and/or bitumens. Anthropogenic inputs of PAHs are low as indicated by low concentrations of combustion PAHs. Alkyl PAH distributions indicate that a significant component of the lower molecular weight PAH fraction is petrogenic. The majority of the high molecular weight PAHs, together with the petrogenic PAHs have a principal source in the Mackenzie River

Separation of benzene from alkanes using 1-ethyl-3-methylpyridinium ethylsulfate ionic liquid at several temperatures and atmospheric pressure: Effect of the size of the aliphatic hydrocarbons

International Nuclear Information System (INIS)

Gonzalez, Emilio J.; Calvar, Noelia; Gomez, Elena; Dominguez, Angeles

2010-01-01

The ionic liquid 1-ethyl-3-methylpyridinium ethylsulfate, [EMpy][ESO 4 ], was studied for the separation of benzene from aliphatic hydrocarbons (octane or nonane) by solvent extraction through the determination of the (liquid + liquid) equilibrium (LLE) of the ternary systems: {octane (1) + benzene (2) + [EMpy][ESO 4 ] (3)} and {nonane (1) + benzene (2) + [EMpy][ESO 4 ] (3)} at T = (283.15 and 298.15) K and atmospheric pressure. Binodal curves were determined using the 'cloud point' method, and tie-line compositions were obtained by density measurements. The values of selectivity and distribution coefficient, derived from the tie-line data, were used to decide if this ionic liquid can be used as potential solvent for the separation of benzene from aliphatic hydrocarbons using liquid extraction. These results were analyzed and compared to those previously reported for the systems {hexane + benzene + [EMpy][ESO 4 ]} and {heptane + benzene + [EMpy][ESO 4 ]}. The experimental results show that this ionic liquid is suitable for the extraction of benzene from mixtures containing octane and nonane. The consistency of tie-line data was ascertained by applying the Othmer-Tobias and Hand equations. The experimental results for the ternary systems were well correlated with the NRTL model. No literature data were found for the mixtures discussed in this paper.

Separation of aliphatic carboxylic acids and benzenecarboxylic acids by ion-exclusion chromatography with various cation-exchange resin columns and sulfuric acid as eluent.

Science.gov (United States)

Ohta, Kazutoku; Ohashi, Masayoshi; Jin, Ji-Ye; Takeuchi, Toyohide; Fujimoto, Chuzo; Choi, Seong-Ho; Ryoo, Jae-Jeong; Lee, Kwang-Pill

2003-05-16

The application of various hydrophilic cation-exchange resins for high-performance liquid chromatography (sulfonated silica gel: TSKgel SP-2SW, carboxylated silica gel: TSKgel CM-2SW, sulfonated polymethacrylate resin: TSKgel SP-5PW, carboxylated polymethacrylate resins: TSKgel CM-5PW and TSKgel OA-Pak A) as stationary phases in ion-exclusion chromatography for C1-C7 aliphatic carboxylic acids (formic, acetic, propionic, butyric, isovaleric, valeric, isocaproic, caproic, 2-methylhexanoic and heptanoic acids) and benzenecarboxylic acids (pyromellitic, trimellitic, hemimellitic, o-phthalic, m-phthalic, p-phthalic, benzoic, salicylic acids and phenol) was carried out using diluted sulfuric acid as the eluent. Silica-based cation-exchange resins (TSKgel SP-2SW and TSKgel CM-2SW) were very suitable for the ion-exclusion chromatographic separation of these benzenecarboxylic acids. Excellent simultaneous separation of these benzenecarboxylic acids was achieved on a TSKgel SP-2SW column (150 x 6 mm I.D.) in 17 min using a 2.5 mM sulfuric acid at pH 2.4 as the eluent. Polymethacrylate-based cation-exchange resins (TSKgel SP-5PW, TSKgel CM-5PW and TSKgel OA-Pak A) acted as advanced stationary phases for the ion-exclusion chromatographic separation of these C1-C7 aliphatic carboxylic acids. Excellent simultaneous separation of these C1-C7 acids was achieved on a TSKgel CM-5PW column (150 x 6 mm I.D.) in 32 min using a 0.05 mM sulfuric acid at pH 4.0 as the eluent.

Aliphatic acetogenin constituents of avocado fruits inhibit human oral cancer cell proliferation by targeting the EGFR/RAS/RAF/MEK/ERK1/2 pathway

Science.gov (United States)

D’Ambrosio, Steven M.; Han, Chunhua; Pan, Li; Kinghorn, A. Douglas; Ding, Haiming

2011-01-01

Avocado (Persea americana) fruits are consumed as part of the human diet and extracts have shown growth inhibitory effects in various types of human cancer cells, although the effectiveness of individual components and their underlying mechanism are poorly understood. Using activity-guided fractionation of the flesh of avocado fruits, a chloroform-soluble extract (D003), was identified that exhibited high efficacy towards premalignant and malignant human oral cancer cell lines. From this extract, two aliphatic acetogenins of previously known structure were isolated, compounds 1 [(2S,4S)-2,4-dihydroxyheptadec-16-enyl acetate] and 2 [(2S,4S)-2,4-dihydroxyheptadec-16-ynyl acetate]. In this study, we show for the first time that the growth inhibitory efficacy of this chloroform extract is due to blocking the phosphorylation of EGFR (Tyr1173), c-RAF (Ser338), and ERK1/2 (Thr202/Tyr204) in the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. Compound 1 and 2 both inhibited phosphorylation of c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204). Compound 2, but not compound 1, prevented EGF-induced activation of EGFR (Tyr1173). When compounds 1 and 2 were combined they synergistically inhibited c-RAF (Ser338) and ERK1/2 (Thr202/Tyr204) phosphorylation, and human oral cancer cell proliferation. The present data suggest that the potential anticancer activity of avocado fruits is due to a combination of specific aliphatic acetogenins that target two key components of the EGFR/RAS/RAF/MEK/ERK1/2 cancer pathway. PMID:21596018

Human breast milk contamination with phthalates and alterations of endogenous reproductive hormones in infants three months of age

DEFF Research Database (Denmark)

Main, Katharina M; Mortensen, Gerda Krog; Kaleva, Marko M

2006-01-01

Phthalates adversely affect the male reproductive system in animals. We investigated whether phthalate monoester contamination of human breast milk had any influence on the postnatal surge of reproductive hormones in newborn boys as a sign of testicular dysgenesis.......Phthalates adversely affect the male reproductive system in animals. We investigated whether phthalate monoester contamination of human breast milk had any influence on the postnatal surge of reproductive hormones in newborn boys as a sign of testicular dysgenesis....

Mono- and diesters from o-phthalic acid in leachates from different European landfills

DEFF Research Database (Denmark)

Jonsson, S.; Eilertsson, J.; Ledin, Anna

2003-01-01

Leachates from 17 different landfills in Europe were, analysed with respect to phthalates, i.e. phthalic acid diesters (PAEs) and their degradation products phthalic acid monoesters (PMEs) and ortho-phthalic acid (PA). Diesters are ubiquitous and the human possible exposure and potential to human...... health and environment has put them in focus. The aim of this study was to elucidate whether monoesters and phthalic acid could be traced in landfill leachates and in what concentrations they may be found. The results showed that phthalates were present in the majority of the leachates investigated....... The monoesters appeared from 1 to 20 mug/L and phthalic acid 2-880 mug/L (one divergent value of 19 mg phthalic acid/L). Their parental diesters were observed from I to 460 mug/L. These observed occurrences of degradation products, of all diesters studied, support that they are degraded under the landfill...

Differences of diurnal variations of some aliphatic and polycyclic aromatic hydrocarbons concentrations in aerosols of the urban area of Madrid

International Nuclear Information System (INIS)

Perez, M. M.; Perez-Pastor, R. M.; Bea, F. J.; Campos, A.; Gonzalez, D.

1991-01-01

A study on daily concentration changes of polycyclic aromatic and aliphatic hydrocarbons (PAH's and AH's), was carried out in aerosols sampled m the Ciudad Universitaria of Madrid. Samples were taken at morning and night during February and June, for short sampling times, on glass fiber filters in Hi-Vol samplers, and then extracted ultrasonically with cyclohexane. Analysis were performed by HRGC with fused-silica capillary columns. The variable traffic rate, and the strong influence during winter periods of domestic heating are characteristic of this place. The aim of this work was to evaluate diurnal and seasonal variations of selected AH and PAH in the urban area of Madrid, by using descriptive parameters, such as total concentrations of AH and PAH, characteristic profiles and predominance carbon index. (Author)

(−-Epigallocatechin 3-Gallate Synthetic Analogues Inhibit Fatty Acid Synthase and Show Anticancer Activity in Triple Negative Breast Cancer

Directory of Open Access Journals (Sweden)

Joan Crous-Masó

2018-05-01

Full Text Available (−-Epigallocatechin 3-gallate (EGCG is a natural polyphenol from green tea with reported anticancer activity and capacity to inhibit the lipogenic enzyme fatty acid synthase (FASN, which is overexpressed in several human carcinomas. To improve the pharmacological profile of EGCG, we previously developed a family of EGCG derivatives and the lead compounds G28, G37 and G56 were characterized in HER2-positive breast cancer cells overexpressing FASN. Here, diesters G28, G37 and G56 and two G28 derivatives, monoesters M1 and M2, were synthesized and assessed in vitro for their cytotoxic, FASN inhibition and apoptotic activities in MDA-MB-231 triple-negative breast cancer (TNBC cells. All compounds displayed moderate to high cytotoxicity and significantly blocked FASN activity, monoesters M1 and M2 being more potent inhibitors than diesters. Interestingly, G28, M1, and M2 also diminished FASN protein expression levels, but only monoesters M1 and M2 induced apoptosis. Our results indicate that FASN inhibition by such polyphenolic compounds could be a new strategy in TNBC treatment, and highlight the potential anticancer activities of monoesters. Thus, G28, G37, G56, and most importantly M1 and M2, are anticancer candidates (alone or in combination to be further characterized in vitro and in vivo.

(-)-Epigallocatechin 3-Gallate Synthetic Analogues Inhibit Fatty Acid Synthase and Show Anticancer Activity in Triple Negative Breast Cancer.

Science.gov (United States)

Crous-Masó, Joan; Palomeras, Sònia; Relat, Joana; Camó, Cristina; Martínez-Garza, Úrsula; Planas, Marta; Feliu, Lidia; Puig, Teresa

2018-05-11

(-)-Epigallocatechin 3-gallate (EGCG) is a natural polyphenol from green tea with reported anticancer activity and capacity to inhibit the lipogenic enzyme fatty acid synthase (FASN), which is overexpressed in several human carcinomas. To improve the pharmacological profile of EGCG, we previously developed a family of EGCG derivatives and the lead compounds G28, G37 and G56 were characterized in HER2-positive breast cancer cells overexpressing FASN. Here, diesters G28, G37 and G56 and two G28 derivatives, monoesters M1 and M2, were synthesized and assessed in vitro for their cytotoxic, FASN inhibition and apoptotic activities in MDA-MB-231 triple-negative breast cancer (TNBC) cells. All compounds displayed moderate to high cytotoxicity and significantly blocked FASN activity, monoesters M1 and M2 being more potent inhibitors than diesters. Interestingly, G28, M1, and M2 also diminished FASN protein expression levels, but only monoesters M1 and M2 induced apoptosis. Our results indicate that FASN inhibition by such polyphenolic compounds could be a new strategy in TNBC treatment, and highlight the potential anticancer activities of monoesters. Thus, G28, G37, G56, and most importantly M1 and M2, are anticancer candidates (alone or in combination) to be further characterized in vitro and in vivo.

An In Silico Knockout Model for Gastrointestinal Absorption Using a Systems Pharmacology Approach - Development and Application for Ketones.

Directory of Open Access Journals (Sweden)

Vittal Shivva

Full Text Available Gastrointestinal absorption and disposition of ketones is complex. Recent work describing the pharmacokinetics (PK of d-β-hydroxybutyrate (BHB following oral ingestion of a ketone monoester ((R-3-hydroxybutyl (R-3-hydroxybutyrate found multiple input sites, nonlinear disposition and feedback on endogenous production. In the current work, a human systems pharmacology model for gastrointestinal absorption and subsequent disposition of small molecules (monocarboxylic acids with molecular weight < 200 Da was developed with an application to a ketone monoester. The systems model was developed by collating the information from the literature and knowledge gained from empirical population modelling of the clinical data. In silico knockout variants of this systems model were used to explore the mechanism of gastrointestinal absorption of ketones. The knockouts included active absorption across different regions in the gut and also a passive diffusion knockout, giving 10 gut knockouts in total. Exploration of knockout variants has suggested that there are at least three distinct regions in the gut that contribute to absorption of ketones. Passive diffusion predominates in the proximal gut and active processes contribute to the absorption of ketones in the distal gut. Low doses are predominantly absorbed from the proximal gut by passive diffusion whereas high doses are absorbed across all sites in the gut. This work has provided mechanistic insight into the absorption process of ketones, in the form of unique in silico knockouts that have potential for application with other therapeutics. Future studies on absorption process of ketones are suggested to substantiate findings in this study.

Amino Acid Insertion Frequencies Arising from Photoproducts Generated Using Aliphatic Diazirines

Science.gov (United States)

Ziemianowicz, Daniel S.; Bomgarden, Ryan; Etienne, Chris; Schriemer, David C.

2017-10-01

Mapping proteins with chemical reagents and mass spectrometry can generate a measure of accessible surface area, which in turn can be used to support the modeling and refinement of protein structures. Photolytically generated carbenes are a promising class of reagent for this purpose. Substituent effects appear to influence surface mapping properties, allowing for a useful measure of design control. However, to use carbene labeling data in a quantitative manner for modeling activities, we require a better understanding of their inherent amino acid reactivity, so that incorporation data can be normalized. The current study presents an analysis of the amino acid insertion frequency of aliphatic carbenes generated by the photolysis of three different diazirines: 3,3'-azibutyl-1-ammonium, 3,3'-azibutan-1-ol, and 4,4'-azipentan-1-oate. Leveraging an improved photolysis system for single-shot labeling of sub-microliter frozen samples, we used EThCD to localize insertion products in a large population of labeled peptides. Counting statistics were drawn from data-dependent LC-MS2 experiments and used to estimate the frequencies of insertion as a function of amino acid. We observed labeling of all 20 amino acids over a remarkably narrow range of insertion frequencies. However, the nature of the substituent could influence relative insertion frequencies, within a general preference for larger polar amino acids. We confirm a large (6-fold) increase in labeling yield when carbenes were photogenerated in the solid phase (77 K) relative to the liquid phase (293 K), and we suggest that carbene labeling should always be conducted in the frozen state to avoid information loss in surface mapping experiments. [Figure not available: see fulltext.

Anaerobic Transformation of Chlorinated Aliphatic Hydrocarbons in a Sand Aquifer Based on Spatial Chemical Distributions

Science.gov (United States)

Semprini, Lewis; Kitanidis, Peter K.; Kampbell, Don H.; Wilson, John T.

1995-04-01

We estimated the distribution of chlorinated aliphatic hydrocarbons (CAHs) from groundwater samples collected along three transects in a sand aquifer. Trichloroethylene (TCE) leaked and contaminated the aquifer probably more than a decade before we collected the measurements. The data show significant concentrations of TCE, cis-l,2-dichloroethylene (c-DCE), vinyl chloride (VC), and ethene. We attributed DCE, VC, and ethene to the reductive dehalogenation of TCE. The CAH concentrations varied significantly with depth and correlate with sulfate and methane concentrations. Anoxic aquifer conditions exist with methane present at relatively high concentrations at depth. High concentrations of TCE correspond with the absence of methane or low methane concentrations, whereas products of TCE dehalogenation are associated with higher methane concentrations and low sulfate concentrations. Indications are that the dechlorination of TCE and DCE to VC and ethene is associated with sulfate reduction and active methanogenesis. TCE dechlorination to DCE is likely occurring under the less reducing conditions of sulfate reduction, with further reductions to VC and ethene occurring under methanogenic conditions. We estimated that about 20% of TCE has dechlorinated to ethene. The analysis of the data enhanced our knowledge of natural in situ transformation and transport processes of CAHs.

Studies on the effect of virtual crosslinking on the hydrolytic stability of novel aliphatic polyurethane ureas for blood contact applications.

Science.gov (United States)

Thomas, V; Jayabalan, M

2001-07-01

The effect of virtual crosslinking on the hydrolytic stability of completely aliphatic novel poly(urethane ureas), HFL9-PU1 (hard-segment content 57.5%) and HFL13-PU2 (hard-segment content 67.9%) based on 4,4'-methylene bis(cyclohexyl isocyanate) (H(12)MDI)-hydroxy-terminated polybutadiene-1,6-hexamethylene diamine, was studied. Fourier transform infrared-attenuated total reflectance and wide-angle X-ray diffraction studies revealed hydrogen-bonding interaction and microphase separation and formation of crystallites by short- and long-range ordering in hard-segment domains. Three-dimensional networks from hydrogen bonding in the present polymers lead to virtually crosslinking and insolubility. These polymers were noncytotoxic to L929 fibroblast cells. The hemolytic potential is below the accepted limit. The studies on in vitro biostability in Ringer's solution, phosphate buffered saline, and papain enzyme revealed no weight loss. The infrared spectral studies revealed changes in the surface, especially on HFL9-PU1 aged in Ringer's solution and phosphate buffered saline, and no changes when aged in papain. The marginal changes noticed in tensile properties were attributed to the changes in degree of hydrogen bonding and associated rearrangement of molecular structure in the bulk. The results revealed that the lesser the crosslinking in virgin polymer, the higher the crosslinking in aged polymer and vice versa. Increased crosslinking during aging provided increased tensile properties in the aged polymer over the virgin polymer and vice versa. For comparison, an aliphatic polyetherurethane urea (HFL16-PU3) was also synthesized using poly(oxy tetra methylene glycol) in addition to the above reactants. Though both HFL9-PU1 and HFL16-PU3 contained the same hard-segment content, the aged sample of the latter showed decreased tensile properties with increased crosslinking during aging in contrast to the former. This was attributed to less microphase separation in the

Skin exposure to aliphatic polyisocyanates in the auto body repair and refinishing industry: II. A quantitative assessment.

Science.gov (United States)

Bello, Dhimiter; Redlich, Carrie A; Stowe, Meredith H; Sparer, Judy; Woskie, Susan R; Streicher, Robert P; Hosgood, H Dean; Liu, Youcheng

2008-03-01

Skin exposure to isocyanates, in addition to respiratory exposures, may contribute to sensitization and asthma. Quantitative skin exposure data are scarce and quantitative methods limited. As part of the Survey of Painters and Repairers of Autobodies by Yale study, a method to sample and quantify human isocyanate skin exposure was developed (based on NIOSH 5525 method) and used to evaluate aliphatic isocyanate skin exposure in 81 auto body shop painters and body technicians. Wipe samples were collected from unprotected skin and from under PPE (gloves, clothing and respirator) using a polypropylene glycol-impregnated wipe. Hexamethylene diisocyanate (HDI), its polyisocyanates [HDI-derived polyisocyanates (pHDI)], isophorone diisocyanate (IPDI) and its polyisocyanates and IPDI-derived polyisocyanates (pIPDI) were quantified separately and also expressed as the total free isocyanate groups (total NCO). For unprotected skin areas, 49 samples were collected for spray painting, 13 for mixing, 27 for paint-related tasks (e.g. sanding and compounding) and 53 for non-paint-related tasks. Forty-three samples were also collected under PPE. The geometric mean (GM) [geometric standard deviation (GSD)] total NCO concentrations (ng NCO cm(-2)) for unprotected skin (hands, face and forearms) was 1.9 (10.9) and range 0.0-64.4. pHDI species were the major contributor to the total NCO content. Levels were very variable, with the highest concentrations measured for clear coating and paint mixing tasks. Isocyanate skin exposure was also commonly detected under PPE, with 92% of samples above the limit of detection. Levels were very variable with the overall GM (GSD) total NCO (ng NCO cm(-2)) under PPE 1.0 (5.2) and range (0.0-47.0) and similar under the different PPE (glove, respirator and clothing). The highest concentrations were detected for mixing and spraying tasks, 6.9 (5.3) and 1.0 (5.2), respectively. Levels under PPE were generally lower than unpaired samples obtained with no

Bi-functional effects of lengthening aliphatic chain of phthalimide-based negative redox couple and its non-aqueous flow battery performance at stack cell

Science.gov (United States)

Kim, Hyun-seung; Hwang, Seunghae; Kim, Youngjin; Ryu, Ji Heon; Oh, Seung M.; Kim, Ki Jae

2018-04-01

Effects of lengthening an aliphatic chain of a phthalimide-based negative redox couple for non-aqueous flow batteries are examined. The working voltage and solubility of N-butylphthalimide are 0.1 V lower and four times greater (2.0 M) than those of methyl-substituted phthalimide. These enhanced properties are attributed to a lower packing density. Consequently, the energy density of the proposed redox couple is greatly enhanced from butyl substitution. Furthermore, the results of the stack flow cell test with N,N,N',N'-tetramethyl-p-phenylenediamine positive redox couple show advantageous features of this non-aqueous flow battery system: a stable Coulombic efficiency and high working voltage.

Ascorbyl palmitate/d-α-tocopheryl polyethylene glycol 1000 succinate monoester mixed micelles for prolonged circulation and targeted delivery of compound K for antilung cancer therapy in vitro and in vivo

Directory of Open Access Journals (Sweden)

Zhang Y

2017-01-01

Full Text Available Youwen Zhang, Deyin Tong, Daobiao Che, Bing Pei, Xiaodong Xia, Gaofeng Yuan, Xin Jin Department of Hospital Pharmacy, The First Hospital of Suqian, Suqian, People’s Republic of China Abstract: The roles of ginsenoside compound K (CK in inhibiting tumor have been widely recognized in recent years. However, low water solubility and significant P-gp efflux have restricted its application. In this study, CK ascorbyl palmitate (AP/d-α-tocopheryl polyethylene glycol 1000 succinate monoester (TPGS mixed micelles were prepared as a delivery system to increase the absorption and targeted antitumor effect of CK. Consequently, the solubility of CK increased from 35.2±4.3 to 1,463.2±153.3 µg/mL. Furthermore, in an in vitro A549 cell model, CK AP/TPGS mixed micelles significantly inhibited cell growth, induced G0/G1 phase cell cycle arrest, induced cell apoptosis, and inhibited cell migration compared to free CK, all indicating that the developed micellar delivery system could increase the antitumor effect of CK in vitro. Both in vitro cellular fluorescence uptake and in vivo near-infrared imaging studies indicated that AP/TPGS mixed micelles can promote cellular uptake and enhance tumor targeting. Moreover, studies in the A549 lung cancer xenograft mouse model showed that CK AP/TPGS mixed micelles are an efficient tumor-targeted drug delivery system with an effective antitumor effect. Western blot analysis further confirmed that the marked antitumor effect in vivo could likely be due to apoptosis promotion and P-gp efflux inhibition. Therefore, these findings suggest that the AP/TPGS mixed micellar delivery system could be an efficient delivery strategy for enhanced tumor targeting and antitumor effects. Keywords: ginsenoside CK, ascorbyl palmitate, TPGS, mixed micelles, anti-tumor therapy

Diatomite-supported Pd-M (M=Cu, Co, Ni) bimetal nanocatalysts for selective hydrogenation of long-chain aliphatic esters.

Science.gov (United States)

Huang, Changliang; Zhang, Hongye; Zhao, Yanfei; Chen, Sha; Liu, Zhimin

2012-11-15

Diatomite supported Pd-M (M=Cu, Co, Ni) bimetal nanocatalysts with various metal compositions were prepared and characterized by means of X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. It was demonstrated that the metal nanoparticles were uniformly distributed on the support, and their size was centered around 8 nm with a relatively narrow size distribution. The catalysts were used to catalyze hydrogenation of long-chain aliphatic esters, including methyl palmitate, methyl stearate, and methyl laurate. It was indicated that the all diatomite-supported Pd-based bimetal catalysts were active to the selective hydrogenation of long-chain esters to corresponding alcohols at 270°C, originated from the synergistic effect between the metal particles and the diatomite support. For the selective hydrogenation of methyl palmitate, Pd-Cu/diatomite with metal loading of 1% and Pd/Cu=3 displayed the highest performance, giving a 1-hexadecanol yield of 82.9% at the substrate conversion of 98.8%. Copyright © 2012 Elsevier Inc. All rights reserved.

Oxidations of N-(3-indoleethyl) cyclic aliphatic amines by horseradish peroxidase: the indole ring binds to the enzyme and mediates electron-transfer amine oxidation.

Science.gov (United States)

Ling, Ke-Qing; Li, Wen-Shan; Sayre, Lawrence M

2008-01-23

Although oxidations of aromatic amines by horseradish peroxidase (HRP) are well-known, typical aliphatic amines are not substrates of HRP. In this study, the reactions of N-benzyl and N-methyl cyclic amines with HRP were found to be slow, but reactions of N-(3-indoleethyl) cyclic amines were 2-3 orders of magnitude faster. Analyses of pH-rate profiles revealed a dominant contribution to reaction by the amine-free base forms, the only species found to bind to the enzyme. A metabolic study on a family of congeneric N-(3-indoleethyl) cyclic amines indicated competition between amine and indole oxidation pathways. Amine oxidation dominated for the seven- and eight-membered azacycles, where ring size supports the change in hybridization from sp3 to sp2 that occurs upon one-electron amine nitrogen oxidation, whereas only indole oxidation was observed for the six-membered ring congener. Optical difference spectroscopic binding data and computational docking simulations suggest that all the arylalkylamine substrates bind to the enzyme through their aromatic termini with similar binding modes and binding affinities. Kinetic saturation was observed for a particularly soluble substrate, consistent with an obligatory role of an enzyme-substrate complexation preceding electron transfer. The significant rate enhancements seen for the indoleethylamine substrates suggest the ability of the bound indole ring to mediate what amounts to medium long-range electron-transfer oxidation of the tertiary amine center by the HRP oxidants. This is the first systematic investigation to document aliphatic amine oxidation by HRP at rates consistent with normal metabolic turnover, and the demonstration that this is facilitated by an auxiliary electron-rich aromatic ring.

Detailed Mechanistic Studies on Palladium-Catalyzed Selective C-H Olefination with Aliphatic Alkenes: A Significant Influence of Proton Shuttling.

Science.gov (United States)

Deb, Arghya; Hazra, Avijit; Peng, Qian; Paton, Robert S; Maiti, Debabrata

2017-01-18

Directing group-assisted regioselective C-H olefination with electronically biased olefins is well studied. However, the incorporation of unactivated olefins has remained largely unsuccessful. A proper mechanistic understanding of olefination involving unactivated alkenes is therefore essential for enhancing their usage in future. In this Article, detailed experimental and computational mechanistic studies on palladium catalyzed C-H olefination with unactivated, aliphatic alkenes are described. The isolation of Pd(II) intermediates is shown to be effective for elucidating the elementary steps involved in catalytic olefination. Reaction rate and order determination, control experiments, isotopic labeling studies, and Hammett analysis have been used to understand the reaction mechanism. The results from these experimental studies implicate β-hydride elimination as the rate-determining step and that a mechanistic switch occurs between cationic and neutral pathway. Computational studies support this interpretation of the experimental evidence and are used to uncover the origins of selectivity.

Tuning different kinds of entangled metal-organic frameworks by modifying the spacer group of aliphatic dicarboxylate ligands and the reactant ratio.

Science.gov (United States)

Yang, Jin-Xia; Zhai, Ji-Quan; Zhang, Xin; Qin, Ye-Yan; Yao, Yuan-Gen

2016-01-14

Taking advantage of the conformational flexibility of the bpp ligand and aliphatic dicarboxylic acids, six interesting entangled coordination polymers, {[Cd(fum)(bpp)(H2O)]·(H2O)}n (), {[Cd(fum)(bpp)2]·(H2O)5}n (), {[Cd2(suc)1.5(bpp)2(NO3)(H2O)2]·6H2O}n (), {[Cd(suc)(bpp)2]·(H2O)1.5}n (), {[Cd2(glu)2(bpp)3]·10H2O}n (), and {Cd(adp)(bpp)(H2O)}n () have been prepared and structurally characterized (bpp = 1,3-bi(4-pyridyl)propane, fum = fumaric, suc = succinate, glu = glutaric, adp = adipic). Compounds and are comprised of undulated 2D 4(4)-sql networks. In the structure of compound , two identical undulated layers are parallelly interpenetrated with each other to give a 2D → 2D interpenetrating framework. For , the dangling arms projected from 2D layers are intercalated into the neighboring sheets, producing a 2D → 3D polythreading framework. Compound shows a rare example of a 2D self-penetrating framework with a (3,4)-connected (4(2)·6(3)·8)(4(2)·6) topology. Compound presents an unusual 2D self-threading network with a novel 4-connected {4(2)·6(3)·8} topology. Compound displays a 3D self-penetrating system based on a 2D → 3D parallel polycatenation array. Compound exhibits an unprecedented 3D self-penetrating structure having both 1D + 1D → 1D polycatenation and 3D + 3D → 3D interpenetration characteristics. A comparison of these six compounds demonstrates that both the different spacer lengths of the aliphatic dicarboxylates and reactant ratios appear to play a significant role in the assembly of entangled frameworks. In addition, thermal stabilities and photoluminescence properties of have been examined in the solid state at room temperature.

[How aliphatic alcohols and ph affect reactional capability of the horse blood serum cholinesterase at its interaction with organophosphorus inhibitors].

Science.gov (United States)

Basova, N E; Kormilitsin, B N; Perchenok, A Iu; Rozengart, E V; Saakov, V S; Suvorov, A A

2013-01-01

There was studied action of aliphatic alcohols (ethanol, propanol, isopropanol, n-butanol, isobutanol, secbutanol, tretbetanol) and pH on various kinds of reactional capability the serum cholinesterase. At the alcohols-affected inhibition of the cholinesterase hydrolytic activity, the determining role was played not the total number carbon atoms in the alcohol molecule, but by the "effective length" of the carbohydrate chain. The fact that the presence of alcohols did not affect parameters of the reverse cholinesterase inhibition with onium ions tetramethylammonium and choline allows suggesting the absence of effect solvents on specific acetylcholine sorption in the enzyme active center. With aid of two rows of hydrophobic organophosphorus inhibitors (OPI), we have managed to estimate both the degree and the character itself of the modifying action of alcohols and pH on the process of irreversible inhibition of serum cholinesterase.

Effect of Difference in Fatty Acid Chain Lengths of Medium- Chain Lipids on Lipid/Surfactant/Water Phase Diagrams and Drug Solubility

Directory of Open Access Journals (Sweden)

Hetal N. Prajapati

2011-09-01

Full Text Available Lipids consisting of medium chain fatty acids are commonly used in the development of lipid-based selfemulsifying and self-microemulsifying drug delivery systems. However, no systematic approach to selecting one lipid over another has been reported in the literature. In this study, propylene glycol (PG monoester (PG monocaprylate, Capmul PG-8® and PG diester (PG dicaprylocaprate, Captex 200P® of C8-fatty acids were compared with PG monoester (PG monolaurate, Capmul PG-12® and PG diester (PG dilaurate, Capmul PG-2L® of C12-fatty acids with respect to their phase diagrams, and especially for their ability to form microemulsions in the presence of a common surfactant, Cremophor EL®, and water. The solubility of two model drugs, danazol and probucol, in the lipids and lipid/surfactant mixtures were also compared. The effect of the chain length of medium-chain fatty acids (C8 versus C12 on the phase diagrams of the lipids was minimal. Both shorter and longer chain lipids formed essentially similar microemulsion and emulsion regions in the presence of Cremophor EL® and water, although the C12-fatty acid esters formed larger gel regions in the phase diagrams than the C8-fatty acid esters. When monoesters were mixed with their respective diesters at 1:1 ratios, larger microemulsion regions with lower lipid particle sizes were observed compared to those obtained with individual lipids alone. While the solubility of both danazol and probucol increased greatly in all lipids studied, compared to their aqueous solubility, the solubility in C12-fatty acid esters was found to be lower than in C8-fatty acid esters when the lipids were used alone. This difference in solubility due to the difference in fatty acid chain length, practically disappeared when the lipids were combined with the surfactant.

Bi-functional effects of lengthening aliphatic chain of phthalimide-based negative redox couple and its non-aqueous flow battery performance at stack cell

Directory of Open Access Journals (Sweden)

Hyun-seung Kim

2018-04-01

Full Text Available Effects of lengthening an aliphatic chain of a phthalimide-based negative redox couple for non-aqueous flow batteries are examined. The working voltage and solubility of N-butylphthalimide are 0.1 V lower and four times greater (2.0 M than those of methyl-substituted phthalimide. These enhanced properties are attributed to a lower packing density. Consequently, the energy density of the proposed redox couple is greatly enhanced from butyl substitution. Furthermore, the results of the stack flow cell test with N,N,N′,N′-tetramethyl-p-phenylenediamine positive redox couple show advantageous features of this non-aqueous flow battery system: a stable Coulombic efficiency and high working voltage.

Long-chain aliphatic beta-diketones from epicuticular wax of Vanilla bean species. Synthesis of nervonoylacetone.

Science.gov (United States)

Ramaroson-Raonizafinimanana, B; Gaydou, E M; Bombarda, I

2000-10-01

Analysis of the neutral lipids from Vanilla fragrans and Vanilla tahitensis (Orchidaceae) without saponification resulted in the isolation and identification of a new product family in this plant: beta-dicarbonyl compounds. The compound structures are composed of a long aliphatic chain with 2,4-dicarbonyl carbons and a cis double bond at the n-9 position. They represent approximately 28% of the neutral lipids, that is, 1.5%, in immature beans, and approximately 10% of the neutral lipids, that is, 0.9%, in mature beans. Using retention indices, gas chromatography-mass spectrometry, derivatization reactions, and chemical degradation, five beta-dicarbonyl compounds have been identified including 16-pentacosene-2,4-dione, 18-heptacosene-2,4-dione, 20-nonacosene-2, 4-dione, 22-hentriacontene-2,4-dione, and 24-tritriacontene-2, 4-dione. Among them (Z)-18-heptacosene-2,4-dione, or nervonoylacetone, has been synthesized in two steps starting from nervonic acid. The major constituent, nervonoylacetone, represented 74.5% of the beta-dicarbonyl fraction. The range of these compounds has been studied in relation with bean maturity for V. fragrans and V. tahitensis species. This compound family has not been found in the leaves or stems of any of the three vanilla species studied and is markedly absent in the beans of V. madagascariensis.

A series of silver(I) coordination polymers with saccarinate and flexible aliphatic diamines

Energy Technology Data Exchange (ETDEWEB)

Yeşilel, Okan Zafer, E-mail: yesilel@ogu.edu.tr [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Karamahmut, Bingül [Department of Chemistry, Faculty of Arts and Sciences, Eskişehir Osmangazi University, 26480 Eskişehir (Turkey); Semerci, Fatih [Department of Energy Systems Engineering, Faculty of Technology, Kırklareli University, 39000 Kırklareli (Turkey); Darcan, Cihan [Department of Molecular Biology and Genetic, Faculty of Arts and Sciences, Bilecik Şeyh Edebali University, Gülümbe-Bilecik (Turkey); Yılmaz, Filiz [Department of Chemistry, Faculty of Sciences, Anadolu University, Eskişehir (Turkey)

2017-05-15

A series of Ag(I) complexes with aliphatic diamines having a different chain length (NH{sub 2}-(CH{sub 2}){sub n}-NH{sub 2}, n=4–9), with the formulas, [Ag(μ-sac)(μ-db){sub 0.5}]{sub n} (1), ([Ag{sub 4}(sac){sub 4}(μ-dp){sub 2}]·4H{sub 2}O){sub n} (2){sub ,} ([Ag{sub 2}(sac){sub 2}(μ-dz)]·2H{sub 2}O){sub n} (3), ([Ag{sub 2}(sac){sub 2}(μ-dh)]·H{sub 2}O){sub n} (4), ([Ag{sub 2}(sac){sub 2}(μ-do)]·H{sub 2}O){sub n} (5a), [Ag{sub 2}(sac){sub 2}(μ-do){sub 2}] (5b) and [Ag{sub 4}(sac){sub 4}(μ-dn){sub 2}]·2H{sub 2}O (6), where sac=saccharinate, db=1,4-diaminobutane, dp=1,5-diaminopentane, dz=1,6-diaminohexane, dh=1,7-diaminoheptane, do=1,8-diaminooctane and dn=1,9-diaminononane, were synthesized and characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction analysis. In 1, the sac ligand bridges adjacent Ag(I) ions through the nitrogen and carbonyl oxygen atoms to form eight-membered bimetallic rings with the Ag···Ag distance being 3.897 Å, which are linked by db ligands to give a 1D zigzag chain. The complexes 2–5a consist of a one-dimensional (1D) linear cationic chains and discrete mononuclear anions. The discreet complex units are further connected by ligand unsupported argentophilic interactions. In 6, the dn ligands bridge adjacent silver centers to form 24-membered macrometallacyclic rings, which are further connected to the anionic [Ag(sac){sub 2}]{sup -} units by argentophilic Ag1···Ag2 interactions to form a tetranuclear structure. The adjacent dinuclear units are further linked together through ligand-unsupported argentophilic Ag···Ag (3.207(1) Å) interactions, generating a one-dimensional linear chain. The most striking feature of complexes is the presence of the rare intermolecular C-H···Ag interactions. In 5b, the do ligand bridges two Ag(I) ions to form a dinuclear with a 22-membered macrometallacyclic ring. Furthermore, biological activities, luminescence properties and thermal analysis (TG

Low dielectric and low surface free energy flexible linear aliphatic alkoxy core bridged bisphenol cyanate ester based POSS nanocomposites

Directory of Open Access Journals (Sweden)

Muthukaruppan eAlagar

2013-10-01

Full Text Available The aim of the present work is to develop a new type of flexible linear aliphatic alkoxy core bridged bisphenol cyanate ester (AECE based POSS nanocomposites for low k applications. The POSS-AECE nanocomposites were developed by incorporating varying weight percentages (0, 5 and 10 wt % of octakis (dimethylsiloxypropylglycidylether silsesquioxane (OG-POSS into cyanate esters. Data from thermal and dielectric studies imply that the POSS reinforced nanocomposite exhibits higher thermal stability and low dielectric value of k=2.4 (10 wt% POSS-AECE4 compared than those of neat AECE. From the contact angle measurement, it is inferred that, the increase in the percentage incorporation of POSS in to AECE, the values of water contact angle was enhanced. Further, the value of surface free energy was lower when compared to that of neat AECE. The molecular level dispersion of POSS into AECE was ascertained from SEM and TEM analyses.

Biodegradable aliphatic-aromatic copolyester/corn starch blend composite reinforced with coffee parchment husk

International Nuclear Information System (INIS)

Silva, Valquiria A.; Teixeira, Jaciele G.; Gomes, Michelle G.; Ortiz, Angel V.; Oliveira, Rene R.; Scapin, Marcos A.; Moura, Esperidiana A.B.; Colombo, Maria A.

2013-01-01

In recent years, studies have shown that the addition of natural fiber or proper filler is an effective strategy for achieving improved properties in biodegradable polymer materials. Moreover, is especially important if such fibers are residues of agro-industrial processes. In this work, a promising technique to develop biodegradable polymer matrix composite based on aliphatic-aromatic copolyester/corn starch blend (Evela®) and coffee parchment husk, which is residue from coffee processing is described. The biodegradable polymeric blend (Evela®) with 5 % (w/w) of ball-milled coffee parchment husk fiber powder, with size ≤250 μm, without any modification was prepared by melt-mixing processing, using a twin screw extruder machine and then pelletized. In a second step, the pelletized Evela®)/coffee parchment (Composite) was then dried at 70 ± 2 deg C for 24 h in a circulating air oven, fed into injection molding machine and test specimens were obtained. The Composite specimen samples were irradiated using an electron beam accelerator, at radiation dose of 20 and 40 kGy, at room temperature in presence of air. The irradiated and non-irradiated samples were characterized by means of scanning electron microscopy (SEM), X-Ray diffraction (XRD), tensile tests and sol-gel analysis and the correlation between their properties was discussed. In addition, coffee parchment husk fiber characterization by SEM, EDS, XRD and WDXRF have also been carried out with a view to evaluate its importance in determining the end-use properties of the composite. (author)

Biodegradable aliphatic-aromatic copolyester/corn starch blend composite reinforced with coffee parchment husk

Energy Technology Data Exchange (ETDEWEB)

Silva, Valquiria A.; Teixeira, Jaciele G.; Gomes, Michelle G.; Ortiz, Angel V.; Oliveira, Rene R.; Scapin, Marcos A.; Moura, Esperidiana A.B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Colombo, Maria A., E-mail: valquiriaalves36@yahoo.com.br [Faculdade de Tecnologia da Zona Leste (FATEC), Sao Paulo, SP (Brazil)

2013-07-01

In recent years, studies have shown that the addition of natural fiber or proper filler is an effective strategy for achieving improved properties in biodegradable polymer materials. Moreover, is especially important if such fibers are residues of agro-industrial processes. In this work, a promising technique to develop biodegradable polymer matrix composite based on aliphatic-aromatic copolyester/corn starch blend (Evela®) and coffee parchment husk, which is residue from coffee processing is described. The biodegradable polymeric blend (Evela®) with 5 % (w/w) of ball-milled coffee parchment husk fiber powder, with size ≤250 μm, without any modification was prepared by melt-mixing processing, using a twin screw extruder machine and then pelletized. In a second step, the pelletized Evela®)/coffee parchment (Composite) was then dried at 70 ± 2 deg C for 24 h in a circulating air oven, fed into injection molding machine and test specimens were obtained. The Composite specimen samples were irradiated using an electron beam accelerator, at radiation dose of 20 and 40 kGy, at room temperature in presence of air. The irradiated and non-irradiated samples were characterized by means of scanning electron microscopy (SEM), X-Ray diffraction (XRD), tensile tests and sol-gel analysis and the correlation between their properties was discussed. In addition, coffee parchment husk fiber characterization by SEM, EDS, XRD and WDXRF have also been carried out with a view to evaluate its importance in determining the end-use properties of the composite. (author)

Differences of diurnal variations of some aliphatic and polycyclic aromatic hydrocarbons concentrations in aerosol of the urban area of Madrid

International Nuclear Information System (INIS)

Perez Garcia, M.M.; Perez Pastor, R.M.; Bea, J.F.; Campos, A.; Gonzalez Diaz, D.

1990-01-01

A study on daily concentration changes of polycyclic aromatic and aliphatic hydrocarbons (PAH's and AH's), was carried out in aerosols sampled in the Ciudad Universitaria of Madrid. Samples were taken at morning and night during February and June, for short sampling times, on glass fiber filters in Hi-Vol samplers, and then extracted ultrasonically with cyclohexane. Analysis were performed by HRGC with fused-silica capillary columns. The variable traffic rate, and the strong influence during winter periods of domestic heating are characteristic of this place. The aim of this work was to evaluate diurnal and seasonal variations of selected AH and PAH in the urban area of Madrid, by using descriptive parameters, such as total concentrations of AH and PAH, characteristic profiles and predominance carbon index. From these results, it has been tried to identify emission sources of the studied hydrocarbons. (Author). 10 refs

The Cer-cqu gene cluster determines three key players in a β-diketone synthase polyketide pathway synthesizing aliphatics in epicuticular waxes

DEFF Research Database (Denmark)

Schneider, Lizette Marais; Adamski, Nikolai M.; Christensen, Caspar Elo

2016-01-01

identification of mutants in their synthesis or transport. The present study discloses three such Eceriferum (cer) genes in barley - Cer-c, Cer-q and Cer-u - known to be tightly linked and functioning in a biochemical pathway forming dominating amounts of β-diketone and hydroxy-β-diketones plus some esterified...... alkan-2-ols. These aliphatics are present in many Triticeae as well as dicotyledons such as Eucalyptus and Dianthus. Recently developed genomic resources and mapping populations in barley defined these genes to a small region on chromosome arm 2HS. Exploiting Cer-c and -u potential functions pinpointed...... five candidates, of which three were missing in apparent cer-cqu triple mutants. Sequencing more than 50 independent mutants for each gene confirmed their identification. Cer-c is a chalcone synthase-like polyketide synthase, designated diketone synthase (DKS), Cer-q is a lipase/carboxyl transferase...

Active site - a site of binding of affinity inhibitors in baker's yeast inorganic pyrophosphatase

International Nuclear Information System (INIS)

Svyato, I.E.; Sklyankina, V.A.; Avaeva, S.M.

1986-01-01

The interaction of the enzyme-substrate complex with methyl phosphate, O-phosphoethanolamine, O-phosphopropanolamine, N-acetylphosphoserine, and phosphoglyolic acid, as well as pyrophosphatase, modified by monoesters of phosphoric acid, with pyrophosphate and tripolyphosphate, was investigated. It was shown that the enzyme containing the substrate in the active site does not react with monophosphates, but modified pyrophosphatase entirely retains the ability to bind polyanions to the regulatory site. It is concluded that the inactivation of baker's yeast inorganic pyrophosphatase by monoesters of phosphoric acid, which are affinity inhibitors of it, is the result of modification of the active site of the enzyme

An atom counting and electrophilicity based QSTR approach

Indian Academy of Sciences (India)

Quantitative-structure-toxicity-relationship (QSTR) models are developed for predicting the toxicity (pIGC50) of 252 aliphatic compounds on Tetrahymena pyriformis. The single parameter models with a simple molecular descriptor, the number of atoms in the molecule, provide reasonable results. Better QSTR models with ...

MORPHOLOGICAL ALTERATIONS OF STAPHYLOCOCCUS AUREUS CAUSED BY ARYL ALIPHATIC AMINOALCOHOL DERIVATIVE

Directory of Open Access Journals (Sweden)

Dronova M.

2015-05-01

Full Text Available Increasing of antimicrobial resistance has created a critical need of the novel antimicrobial agents. One of the promising chemical classes for its development are aryl aliphatic aminoalcohols. New compounds of this class were synthesized at the Institute of organic chemistry (Kiev, Ukraine, by Y. Korotkiy. After the screening studies compound KVM-194 was selected as the potent antistaphylococcal agent. The aim of the study was to examine ultrastructural changes in the bacterial cells under the influence of the compound KVM-194. Materials and methods. Staphylococcus aureus ATCC 25923 was used in all experiments. The minimum inhibitory concentration was determined by serial macrodilution method in Mueller-Hinton broth. Bacteria were exposed to the 0,5 MIC and 5 MICs of the KVM- 194 for 1 h and 24 h. Ultrastructure of intact and treated Staphylococcus aureus cells was examined by transmission electron microscopy after contrasting by osmium tetraoxide and lead citrate. Results and Discussion. The compound KVM-194 possesses a distinct antibacterial activity against Staphylococcus aureus, the minimum inhibitory concentration is 1.25 μg/ml. We found that exposure to KVM-194 at a subinhibitory concentration resulted in alterations of the cell morphology even after 1 h of treatment. The roughness of the cell surface and emerging of the intracellular particles of different electron density were observed. Increase of the incubation time to 24 h led to detachment of membrane from cytoplasm, multimembrane structures within cells emergence and formation of nonpolar septum. 1 h exposition to suprainhibitory concentration of KVM-194 resulted in nucleoid fragmentation, septum abnormalities and necrosis of some cells. We found that increasing of the incubation period to 24 h led to exacerbation of alterations: cell wall rupture, leakage of cytoplasm and a large number of lysed cells were registered. Conclusion. Observed alterations, suggest the possible

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

Science.gov (United States)

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.

Gamma-aminobutyric acid esters. 1. Synthesis, brain uptake, and pharmacological studies of aliphatic and steroid esters of gamma-aminobutyric acid

International Nuclear Information System (INIS)

Shashoua, V.E.; Jacob, J.N.; Ridge, R.; Campbell, A.; Baldessarini, R.J.

1984-01-01

Labeled and unlabeled aliphatic and steroid esters of gamma-amino[U- 14 C]butyric acid (GABA) were synthesized and tested for their capacity to penetrate the blood-brain barrier and for evidence of central neuropharmacological activity in rodents. The uptake of the labeled 9,12,15-octadecatrienyl (linolenyl), 3-cholesteryl, 1-butyl, and the 9-fluoro-11 beta,17-dihydroxy-16 alpha-methyl-3,20-dioxopregna -1,4-dien-21-yl (dexamethasone) esters of GABA into mouse brain increased 2-, 25-, 74-, and 81-fold over GABA, respectively. The cholesteryl ester of GABA depressed the general motor activity of mice and rats in a dose-dependent manner, whereas the 1-butyl, linolenyl, and dexamethasone esters were inactive by this test. Studies of the rates of hydrolysis, GABA receptor binding capacity, and octanol/water partition coefficients indicated that pharmacological activity of the esters after entry into the central nervous system (CNS) was dependent on their capacity to release GABA by enzymatic hydrolysis and their lipid solubility

Zinc oxide/polypyrrole nanocomposite as a novel solid phase microextraction coating for extraction of aliphatic hydrocarbons from water and soil samples

International Nuclear Information System (INIS)

Amanzadeh, Hatam; Yamini, Yadollah; Moradi, Morteza

2015-01-01

Highlights: • ZnO/polypyrrole (ZNO/PPY) nanocomposite coating was fabricated on stainless steel. • Nanocomposite coating morphology was evaluated using scanning electron microscopy. • It was applied for HS-SPME of aliphatic hydrocarbons in water and soil samples. • Separation and determination of the hydrocarbons were performed by GC-FID. • The method is suitable for routine analysis of n-alkanes in various environmental samples. - Abstract: In this work, ZnO/PPy nanocomposite coating was fabricated on stainless steel and evaluated as a novel headspace solid phase microextraction (HS-SPME) fiber coating for extraction of ultra-trace amounts of environmental pollutants; namely, aliphatic hydrocarbons in water and soil samples. The ZnO/PPy nanocomposite were prepared by a two-step process including the electrochemical deposition of PPy on the surface of stainless steel in the first step, and the synthesis of ZnO nanorods by hydrothermal process in the pores of PPy matrix in the second step. Porous structure together with ZnO nanorods with the average diameter of 70 nm were observed on the surface by using scanning electron microscopy (SEM). The effective parameters on HS-SPME of hydrocarbons (i.e., extraction temperature, extraction time, desorption temperature, desorption time, salt concentration, and stirring rate) were investigated and optimized by one-variable-at-a-time method. Under optimized conditions (extraction temperature, 65 ± 1 °C; extraction time, 15 min; desorption temperature, 250 °C; desorption time, 3 min; salt concentration, 10% w/v; and stirring rate, 1200 rpm), the limits of detection (LODs) were found in the range of 0.08–0.5 μg L −1 , whereas the repeatability and fiber-to-fiber reproducibility were in the range 5.4–7.6% and 8.6–10.4%, respectively. Also, the accuracies obtained for the spiked n-alkanes were in the range of 85–108%; indicating the absence of matrix effects in the proposed HS-SPME method. The results

Zinc oxide/polypyrrole nanocomposite as a novel solid phase microextraction coating for extraction of aliphatic hydrocarbons from water and soil samples

Energy Technology Data Exchange (ETDEWEB)

Amanzadeh, Hatam; Yamini, Yadollah [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175 Tehran (Iran, Islamic Republic of); Moradi, Morteza [Department of Semiconductors, Materials and Energy Research Center, Karaj (Iran, Islamic Republic of)

2015-07-16

Highlights: • ZnO/polypyrrole (ZNO/PPY) nanocomposite coating was fabricated on stainless steel. • Nanocomposite coating morphology was evaluated using scanning electron microscopy. • It was applied for HS-SPME of aliphatic hydrocarbons in water and soil samples. • Separation and determination of the hydrocarbons were performed by GC-FID. • The method is suitable for routine analysis of n-alkanes in various environmental samples. - Abstract: In this work, ZnO/PPy nanocomposite coating was fabricated on stainless steel and evaluated as a novel headspace solid phase microextraction (HS-SPME) fiber coating for extraction of ultra-trace amounts of environmental pollutants; namely, aliphatic hydrocarbons in water and soil samples. The ZnO/PPy nanocomposite were prepared by a two-step process including the electrochemical deposition of PPy on the surface of stainless steel in the first step, and the synthesis of ZnO nanorods by hydrothermal process in the pores of PPy matrix in the second step. Porous structure together with ZnO nanorods with the average diameter of 70 nm were observed on the surface by using scanning electron microscopy (SEM). The effective parameters on HS-SPME of hydrocarbons (i.e., extraction temperature, extraction time, desorption temperature, desorption time, salt concentration, and stirring rate) were investigated and optimized by one-variable-at-a-time method. Under optimized conditions (extraction temperature, 65 ± 1 °C; extraction time, 15 min; desorption temperature, 250 °C; desorption time, 3 min; salt concentration, 10% w/v; and stirring rate, 1200 rpm), the limits of detection (LODs) were found in the range of 0.08–0.5 μg L{sup −1}, whereas the repeatability and fiber-to-fiber reproducibility were in the range 5.4–7.6% and 8.6–10.4%, respectively. Also, the accuracies obtained for the spiked n-alkanes were in the range of 85–108%; indicating the absence of matrix effects in the proposed HS-SPME method. The results

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

Science.gov (United States)

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. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Esters of 3-chloro-1,2-propanediol (3-MCPD) in vegetable oils: significance in the formation of 3-MCPD.

Science.gov (United States)

Seefelder, W; Varga, N; Studer, A; Williamson, G; Scanlan, F P; Stadler, R H

2008-04-01

3-Mono-chloropropane-1,2-diol (3-MCPD) is a contaminant that occurs in food in its free (diol) form as well as in an esterified (with fatty acids) form. Using a simple intestinal model, it was demonstrated that 3-MCPD monoesters and 3-MCPD diesters are accepted by intestinal lipase as substrates in vitro. Under the chosen conditions, the yield of 3-MCPD from a 3-MCPD monoester was greater than 95% in approximately 1 min. Release from the diesters was slower, reaching about 45, 65 and 95% of 3-MCPD after 1, 5 and 90 min of incubation, respectively. However, in human, the hydrolysis of 3-MCPD esters is unlikely to release 100% as 3-MCPD, as triglycerides and phospholipids are hydrolysed in the intestine liberating 2-monoglycerides. Assuming a similar metabolism for 3-MCPD esters as that known for acylglycerols in humans in vivo, the de-esterification in positions 1 and 3 would thus be favoured by pancreatic lipases. Therefore, 3-MCPD, and 3-MCPD-2 monoesters would be released, respectively, from the 1-/3-monoesters, and the diesters potentially present in food. Hence, information on the exact amounts of the partial fatty acid chloroesters, i.e. 3-MCPD mono- and diesters, is important to assess the contribution of foods to the bioavailability of 3-MCPD. Therefore, a rapid method for the determination of the ratio of 3-MCPD monoesters to diesters in fats and oils was developed using gas chromatography-mass spectrometry (GC-MS) and isotopically labelled 3-MCPD esters as internal standards. The analysis of 11 different samples of fat mixes typically employed in food manufacturing demonstrated that a maximum of about 15% of the total amount of 3-MCPD bound in esters is present in the monoesterified form. The potentially slower release of 3-MCPD from 3-MCPD diesters, and the mono- to diesters ratio suggest that 3-MCPD esters may in fact contribute only marginally to the overall dietary exposure to 3-MCPD. Further work on the bioavailability, metabolism and possible

Effect of processing on the alkaloids in Aconitum tubers by HPLC-TOF/MS

Directory of Open Access Journals (Sweden)

Min Liu

2017-06-01

Full Text Available According to the Chinese Pharmacopoeia 2015, only processed Aconitum tubers can be clinically applied, and the effect of processing is unclear. This research aimed to explore the effect of processing on cardiac efficacy of alkaloids in Aconitum tubers. First, the chemical ingredients in unprocessed and processed Aconitum tubers were identified and compared by using high performance liquid chromatography time-of-flight mass spectrometry (HPLC-TOF/MS and multivariate pattern recognition methods. Then the representative alkaloids in Aconitum tubers, aconitine, benzoylaconine, and aconine, which belong to diester-diterpenoid alkaloids, monoester-diterpenoid alkaloids, and amine-diterpenoid alkaloids, respectively, were selected for further validation of attenuated mechanism. Subsequent pharmacological experiments with aconitine, benzoylaconine, and aconine in SD rats were used for validate the effect of processing on cardiac functions. After processing the Aconitum tubers, it was found that the contents of diester-diterpenoid alkaloids were reduced, and those of monoester-diterpenoid alkaloids and amine-diterpenoid alkaloids were increased, suggesting that diester-diterpenoid alkaloids were transformed into monoester-diterpenoid alkaloids and amine-diterpenoid alkaloids. Through further decocting the aconitine in boiling water, it was confirmed that the three alkaloids could be progressively transformed. Pharmacological experiments with aconitine, benzoylaconine, and aconine in SD rats showed that aconitine at a dose of 0.01 mg/kg and aconine at a dose of 10 mg/kg enhanced the cardiac function, while benzoylaconine at a dose of 2 mg/kg weakened the cardiac function. The effect of processing is attributed to the transformation of the most toxic diester-diterpenoid alkaloids into less toxic monoester-diterpenoid alkaloids and amine-diterpenoid alkaloids.

Chemical Studies of Yellow Tamarillo (Solanum betaceum Cav. Fruit Flavor by Using a Molecular Sensory Approach

Directory of Open Access Journals (Sweden)

Juliana María García

2016-12-01

Full Text Available The odor-active volatile compounds of yellow tamarillo fruit (S. betaceum Cav. were identified and quantified by using a sensomics approach, combining a gentle volatile extraction (solvent-assisted flavor evaporation (SAFE, gas chromatography-mass spectrometry (GC-MS, and sensory analyses (gas chromatography-olfactometry (GC-O and aroma extract dilution analysis (AEDA. The medium-term purpose of this work is to evaluate the change of odor-active volatiles during processing. Thus, (Z-3-hexenal, hexanal, and ethyl butanoate were identified as key aroma compounds of yellow tamarillo. The C6-aliphatic compounds, aliphatic esters, and terpenols were characterized as the volatiles responsible for the herbal-green, fruity, and fresh-mint odor notes of this variety, respectively. Additionally, one non-volatile compound contributing to the residual bitter taste of this fruit was isolated by a bioguided (taste sensory analyses fractionation. The freeze-dried fruit was sequentially liquid-liquid partitioned with solvents of different polarity, and then the ethyl acetate fraction was submitted to size exclusion chromatography. Then, its structure was elucidated as rosmarinic acid, by using common spectroscopic methods (mass spectrometry (MS and nuclear magnetic resonance (NMR. The amount of rosmarinic acid was quantified as 46.17 ± 1.20 mg/100 g of dried fruit, by the external standard method. Its bitter taste threshold value was determined by using the 3AFC (alternative forced choice method to be 37.00 ± 1.25 mg/L.

Novel lipid constituents identified in seeds of Nigella sativa (Linn)

International Nuclear Information System (INIS)

Mehta, B.K.; Verma, Manjul; Gupta, Meenal

2008-01-01

Novel lipids were isolated from the unsaponifiable matter extracted from seeds of Nigella sativa Linn by using n-hexane. The new dienoate and two monoesters were the new lipids identified by spectral (IR, 1 H- and 13 C-NMR spectra, mass spectrum, elemental analysis) and chemical analysis. The dienoate (1) was identified as methylnonadeca-15,17-dienoate and two monoesters were identified as pentyl hexadec-12-enoate (2) and pentyl pentadec-11-enoate (3). Linoleic acid, oleic acid, β-sitosterol and stigmasterol were identified as part of the lipid structures. All compounds exhibited moderate activity against Staphylococcus aureus and poor activity against shigella spp, and Klebsiella pneumoniae. (author)

Novel lipid constituents identified in seeds of Nigella sativa (Linn)

Energy Technology Data Exchange (ETDEWEB)

Mehta, B.K.; Verma, Manjul; Gupta, Meenal [Vikram University (India). School of Studies in Chemistry and Biochemistry]. E-mail: bkmehta11@yahoo.com

2008-07-01

Novel lipids were isolated from the unsaponifiable matter extracted from seeds of Nigella sativa Linn by using n-hexane. The new dienoate and two monoesters were the new lipids identified by spectral (IR, {sup 1}H- and {sup 13}C-NMR spectra, mass spectrum, elemental analysis) and chemical analysis. The dienoate (1) was identified as methylnonadeca-15,17-dienoate and two monoesters were identified as pentyl hexadec-12-enoate (2) and pentyl pentadec-11-enoate (3). Linoleic acid, oleic acid, {beta}-sitosterol and stigmasterol were identified as part of the lipid structures. All compounds exhibited moderate activity against Staphylococcus aureus and poor activity against shigella spp, and Klebsiella pneumoniae. (author)

Report on three aliphatic dimethylarsinoyl compounds as common minor constituents in marine samples. An investigation using high-performance liquid chromatography inductively coupled plasma mass spectrometry and electrospray ionisation tandem mass spectrometry

DEFF Research Database (Denmark)

Sloth, Jens Jørgen; Larsen, Erik Huusfeldt; Julshamn, K.

2005-01-01

for the structures of the three compounds. The concentrations of the three arsenicals were determined in 37 marine organisms comprising algae, crustaceans, bivalves, fish and mammals by HPLC/ICPMS. The three arsenicals DMAA, DMAE and DMAP, which occurred at mug kg(-1) concentrations, were detected in 25, 23 and 17......Three water-soluble aliphatic arsenicals, dimethylarsinoyl acetate (DMAA), dimethylarsinoyl ethanol (DMAE), and dimethylarsinoyl propionate (DMAP), were identified in marine biological samples. Sample extracts in methanol/water (1 + 1) were analysed by cation-exchange high-performance liquid...

Microtropins A-I: 6'-O-(2″S,3″R)-2″-ethyl-2″,3″-dihydroxybutyrates of aliphatic alcohol β-D-glucopyranosides from the branches of Microtropis japonica.

Science.gov (United States)

Uemura, Yuka; Sugimoto, Sachiko; Matsunami, Katsuyoshi; Otsuka, Hideaki; Takeda, Yoshio; Kawahata, Masatoshi; Yamaguchi, Kentaro

2013-03-01

From the branches of Microtropis japonica (Celastraceae), nine aliphatic glucosides, named microtropins A-I, were isolated. The 6-position of glucose was esterified with (2S,3R)-2-ethyl-2,3-dihydroxybutyric acid. Microtropins A-D contained a rare natured product nitrile functional group in their aglycones. The absolute structures of the (2S,3R)-2-ethyl-2,3-dihydroxybutyric acid moiety and aglycone of microtropin A were determined by an X-ray crystallographic method. Copyright © 2012 Elsevier Ltd. All rights reserved.

High-resolution gas chromatographic analysis of polycyclic aromatic hydrocarbons and aliphatic hydrocarbons; Separacion por cromatografia de gases de alta eficiencia de hidrocarburos aromaticos policiclicos, (PAH) y alifaticos (AH) ambientales, empleado como fases estacionarias OV-1 y SE-54

Energy Technology Data Exchange (ETDEWEB)

Perez, M.; Gonzalez, D.

1988-07-01

A study of the analysis by gas chromatography of aromatic polycyclic hydrocarbons and aliphatic hydrocarbons is presented. The separation has been carried out by glass and fused silica capillary column in two different polar stationary phases OV-1 and SE-54. The limitation and the advantages of the procedure are discussed in terms of separation, sensitivity and precision. (Author) 20 refs.

Correlations Between retention indices and molecular structure of aliphatic alcohols and of their benzoyl derivatives on phenyl substituted polysiloxane stationary phases

International Nuclear Information System (INIS)

Pias, J. B.; Gasco, L.

1976-01-01

The retention indices of aliphatic alcohols of carbon number up to C g , and of their benzoyl derivatives up to C 7 , were determined in columns packed with Chromo sorb G (AW-DMCS-HP) coated previously with 5% methyl, and methyl phenyl polysiloxanes with increasing polarity (SE-30, 0V-3, 0V-7, 0V-11, 0V-17 and OV-25). Correlations between retention indices and chain length for 1-alcohols, 2-alcohols, 3-alcohols, 1 , on -3-alcohols, 2-methyl-1-alcohols and for their corresponding benzoyl derivatives were calculated at 100, 120 and 140 degree centigree. In alcohols, a -CH 2 - group increases I approximately 100 units, and in their benzoyl derivatives from 80 to 100 units. Dispersion indices Δl , and positional and structural increments δI, were evaluated for -OH and benzoyl groups in terms of phase polarity and chain length. Effects of chain length, chain branching and double bond location on retention parameters were also studied. (Author) 23 refs

Assessment of degradation potential of aliphatic hydrocarbons by autochthonous filamentous fungi from a historically polluted clay soil.

Science.gov (United States)

Covino, Stefano; D'Annibale, Alessandro; Stazi, Silvia Rita; Cajthaml, Tomas; Čvančarová, Monika; Stella, Tatiana; Petruccioli, Maurizio

2015-02-01

The present work was aimed at isolating and identifying the main members of the mycobiota of a clay soil historically contaminated by mid- and long-chain aliphatic hydrocarbons (AH) and to subsequently assess their hydrocarbon-degrading ability. All the isolates were Ascomycetes and, among them, the most interesting was Pseudoallescheria sp. 18A, which displayed both the ability to use AH as the sole carbon source and to profusely colonize a wheat straw:poplar wood chip (70:30, w/w) lignocellulosic mixture (LM) selected as the amendment for subsequent soil remediation microcosms. After a 60 d mycoaugmentation with Pseudoallescheria sp. of the aforementioned soil, mixed with the sterile LM (5:1 mass ratio), a 79.7% AH reduction and a significant detoxification, inferred by a drop in mortality of Folsomia candida from 90 to 24%, were observed. However, similar degradation and detoxification outcomes were found in the non-inoculated incubation control soil that had been amended with the sterile LM. This was due to the biostimulation exerted by the amendment on the resident microbiota, fungi in particular, the activity and density of which were low, instead, in the non-amended incubation control soil. Copyright © 2014 Elsevier B.V. All rights reserved.

Analysis of TPH and Aliphatic and Aromatic Hydrocarbons Fractions in Environmental Interest Matrices; Analisis del TPH y las Fracciones de Hidrocarburos Alifaticos y Aromaticos en Matrices de Interes Medioambiental

Energy Technology Data Exchange (ETDEWEB)

Pindado, O.; Perez, R. M.; Garcia, S.

2014-02-01

Analytical methods to analyze TPH and several aliphatic and aromatic fractions present in soil and groundwater samples contaminated by hydrocarbons are showed. As a part of BIOXISOIL project, analyzing these parameters is fundamental and indispensable to know the initial contamination level, design an adequate method to decontaminate it and eventually assess decontamination accomplished. Analysis of both matrices involve different extraction stages such as microwave radiation, clean up steps based on solid phase extraction and finally a chromatograph analysis with flame ion detector. Analytical procedures have showed satisfactory analytical quality parameters and have been validated against several certified reference materials. (Author)

Hybrid structures formed by homo- and heteroleptic aliphatic dicarboxylates of lead with 2-D inorganic connectivity

International Nuclear Information System (INIS)

Thirumurugan, A.; Rao, C.N.R.

2008-01-01

Three-dimensional homoleptic (single type of ligand) lead dicarboxylates with hybrid structures involving Pb-O-Pb linkages of the compositions, Pb(C 5 H 6 O 4 ), I, and Pb(C 6 H 8 O 4 ), II and III, have been synthesized and characterized. Three-dimensional heteroleptic (mixed ligands) lead dicarboxylates of the formulae, Pb 2 (C 2 O 4 )(C 4 H 4 O 4 ), IV and Pb 2 (C 2 O 4 )(C 6 H 8 O 4 ), V, with hybrid structures involving Pb-O-Pb linkages have also been prepared and characterized along with a novel two-dimensional lead nitrate-oxalate of the composition, (OPb 2 ) 2 (C 2 O 4 )(NO 3 ) 2 , VI. In all these dicarboxylates, there is two-dimensional inorganic connectivity and the lead (II) cation has hemi- or holo-directed coordination geometry. Depending upon the torsional angle and the coordination mode of the dicarboxylate anions as well as the geometry of the lead (II) cations, these hybrid compounds exhibit two types of two-dimensional inorganic connectivities. - Graphical abstract: Three homoleptic and two heteroleptic three-dimensional lead aliphatic dicarboxylates along with a novel two-dimensional lead nitrate-oxalate with hybrid structures involving Pb-O-Pb linkages have been synthesized and charecterized. In all these dicarboxylates, there is two-dimensional inorganic connectivity. The lead (II) cation has hemi- or holo-directed coordination geometry

Inventory, distribution, and origin of aliphatic and polyaromatic hydrocarbons in sea water, the surface microlayer, and the aerosols in the tropical Eastern Atlantic

Energy Technology Data Exchange (ETDEWEB)

Marty, J C; Saliot, A; Tissier, M J

1978-03-20

Hydrocarbons have been analyzed in several samples from ''Midlante'' cruise, Cape Verde islands-Canary islands, in the Eastern tropical Atlantic: subsurface water, sea surface microlayer collected by a metallic screen and aerosols collected by filtration of large air volumes at about 12 m. above the sea surface. Detailed analysis of aliphatic and polyaromatic hydrocarbons has been made by computerized gas chromatography/mass spectrometry. This study of the air/sea interface indicates a discontinuity in hydrocarbon composition between the underlying water and the microlayer and a similarity between the surface microlayer and the aerosols. The origin of the collected aerosols is essentially marine with a minor terrestrial contribution. The hydrocarbon pattern shows that, superimposed on the typical marine components, a contribution from smokes of natural and industrial origin and/or from pollution associated with crude oil sea slicks is present.

Characterization of phosphorus forms in lake macrophytes and algae by solution (31)P nuclear magnetic resonance spectroscopy.

Science.gov (United States)

Feng, Weiying; Zhu, Yuanrong; Wu, Fengchang; Meng, Wei; Giesy, John P; He, Zhongqi; Song, Lirong; Fan, Mingle

2016-04-01

Debris from aquatic macrophytes and algae are important recycling sources of phosphorus (P), which can result in continuing blooms of algae by recycling bioavailable P in the eutrophic lakes. However, knowledge of forms of P in aquatic macrophytes and algae and their contribution to internal loads of P in lakes is limited. Without such knowledge, it is difficult to develop appropriate strategies to remediate and or restore aquatic ecosystems that have become eutrophic. Therefore, in this work, P was extracted from six types of aquatic macrophytes and algae collected from Tai Lake of China and characterized by use of solution (31)P-nuclear magnetic resonance (NMR) spectroscopy. When extracted by 0.5 M NaOH-25 mM EDTA, extraction recovery of total P(TP) and organic P(Po) exceeded 90 %. Concentrations of Po in algae and aquatic macrophytes were 5552 mg kg(-1) and 1005 mg kg(-1) and accounted for 56.0 and 47.2 % of TP, respectively. When Po, including condensed P, was characterized by solution (31)P-NMR Po in algae included orthophosphate monoesters (79.8 %), pyrophosphate (18.2 %), and orthophosphate diester (2.0 %), and Po in aquatic macrophytes included orthophosphate monoesters (90.3 %), pyrophosphate (4.2 %), and orthophosphate diester (5.5 %). Additionally, orthophosphate monoesters in algal debris mainly included β-glycerophosphate (44.1 %), α-glycerophosphate (13.5 %), and glucose 6-phosphate (13.5 %). Orthophosphate monoesters in aquatic macrophytes mainly included β-glycerophosphate (27.9 %), α-glycerophosphate (24.6 %), and adenosine 5' monophosphate (8.2 %). Results derived from this study will be useful in better understanding nutrient cycling, relevant eutrophication processes, and pollution control for freshwater lakes.

Analysis of dechlorination kinetics of chlorinated aliphatic hydrocarbons by Fe(II) in cement slurries

Energy Technology Data Exchange (ETDEWEB)

Jung, Bahngmi [Department of Earth and Environmental Sciences, Wright State University, Dayton, OH 45435-0001 (United States)], E-mail: jung.bahngmi@gmail.com; Batchelor, Bill [Department of Civil Engineering, Texas A and M University, College Station, TX 77843-3136 (United States)

2008-03-21

Degradative solidification/stabilization with ferrous iron (DS/S-Fe(II)) has been found to be effective in degrading a number of chlorinated aliphatic hydrocarbons including 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), tetrachloroethylene (PCE), trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC), carbon tetrachloride (CT) and chloroform (CF). Previous studies have characterized degradation kinetics in DS/S-Fe(II) systems as affected by Fe(II) dose, pH and initial target organic concentration. The goal of this study is to investigate the importance of various chemical properties on degradation kinetics of DS/S-Fe(II). This was accomplished by first measuring rate constants for degradation of 1,1,1-TCA, 1,1,2,2-TeCA and 1,2-dichloroethane (1,2-DCA) in individual batch experiments. Rate constants developed in these experiments and those obtained from the literature were related to thermodynamic parameters including one-electron reduction potential, two-electron reduction potential, bond dissociation energy and lowest unoccupied molecular orbital energies. Degradation kinetics by Fe(II) in cement slurries were generally represented by a pseudo-first-order rate law. The results showed that the rate constants for chlorinated methanes (e.g. CT, CF) and chlorinated ethanes (e.g. 1,1,1-TCA) were higher than those for chlorinated ethylenes (e.g. PCE, TCE, 1,1-DCE and VC) under similar experimental conditions. The log of the pseudo-first-order rate constant (k) was found to correlate better with lowest unoccupied molecular orbital energies (E{sub LUMO}) (R{sup 2} = 0.874) than with other thermodynamic parameter descriptors.

STRUCTURAL PHASE TRANSITION OF ALIPHATIC NYLONS VIEWED FROM THE WAXD/SAXS AND VIBRATIONAL SPECTRAL MEASUREMENTS AND MOLECULAR DYNAMICS CALCULATION

Institute of Scientific and Technical Information of China (English)

Kohji Tashiro

2007-01-01

The crystalline phase transition of aliphatic nylon 10/10 has been investigated on the basis of the simultaneous measurement of wide-angle and small-angle X-ray scatterings, the infrared spectral measurement and the molecular dynamics calculation. An interpretation of infrared spectra taken for a series of nylon samples and the corresponding model compounds was successfully made, allowing us to assign the infrared bands of the planar-zigzag methylene segments reasonably. As a result the methylene segmental parts of molecular chains were found to experience an order-to-disorder transition in the Brill transition region, where the intermolecular hydrogen bonds are kept alive although the bond strength becomes weaker at higher temperature. The small-angle X-ray scattering data revealed a slight change in lamellar stacking mode in the transition region. The crystal structure has been found to change more remarkably in the temperature region immediately below the melting point, where the conformationally disordered chains experienced drastic rotational and translational motions without any constraints by hydrogen bonds, and the lamellar thickness increased largely along the chain axis. These experimental results were reasonably reproduced by the molecular dynamics calculation performed at the various temperatures.

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

Science.gov (United States)

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.

Direct determination of 3-chloropropanol esters in edible vegetable oils using high resolution mass spectrometry (HRMS-Orbitrap).

Science.gov (United States)

Graziani, Giulia; Gaspari, Anna; Chianese, Donato; Conte, Lanfranco; Ritieni, Alberto

2017-11-01

A series of refined edible oils derived from mixed seeds, peanuts, corn, sunflower and palm obtained from the local supermarket were analyzed for their content of 3-MCPD esters. A direct analytical method for the determination of 3-monochloropropane-1,2-diol esters (3-MCPD esters) was applied to investigate the major MCPD esters found in common edible oils; in particular seven types of monoesters and eleven types of diesters were detected. The limits of detection (LODs) for monoesters and diesters of 3-MCPD were in the range of 0.079-12.678 µg kg -1 and 0.033-18.610 µg kg -1 in edible oils, and the ranges of limits of quantitation (LOQs) were 0.979-38.035 µg kg -1 and 0.100-55 µg kg -1 , respectively. The recoveries of 3-MCPD esters from oil samples were in the range of 80-100%, with RSD ranging between 1.9 and 11.8%. The concentration levels of total 3-MCPD diesters in vegetable oil samples were in the range from 0.106 up to 3.444 μg g -1 whereas total monoesters ranged from 0.005 up to 1.606 μg g -1 .

Identifying the source of petroleum pollution in sediment cores of southwest of the Caspian Sea using chemical fingerprinting of aliphatic and alicyclic hydrocarbons.

Science.gov (United States)

Shirneshan, Golshan; Bakhtiari, Alireza Riyahi; Memariani, Mahmoud

2017-02-15

In this study, the concentration and sources of aliphatic and petroleum markers were investigated in 105 samples of Anzali, Rezvanshahr and Astara cores from the southwest of Caspian Sea. Petroleum importation was diagnosed as a main source in most depths of cores by the results of unresolved complex mixture, carbon preference index and hopanes and steranes. From the chemical diagnostic parameters, petroleum inputs in sediment of cores were determined to be different during years and the sources of hydrocarbons in some sections differed than Anzali and Turkmenistan and Azerbaijan oils. Diagenic ratios in most sediments of upper and middle sections in Astara core were determined to be highly similar to those of Azerbaijan oil, while the presence of Turkmenistan and Anzali oils were detected in a few sections of Anzali and Rezvanshahr cores and only five layers of downer section in Anzali core, respectively. Copyright © 2016. Published by Elsevier Ltd.

Polymeric nanoparticles developed by vitamin E-modified aliphatic polycarbonate polymer to promote oral absorption of oleanolic acid

Directory of Open Access Journals (Sweden)

Wenjuan Zhang

2017-11-01

Full Text Available Oleanolic acid (OA exhibited good pharmacological activities in the clinical treatment of hypoglycemia, immune regulation, acute jaundice and chronic toxic hepatitis. However, the oral delivery of OA is greatly limited by its inferior water solubility and poor intestinal mucosa permeability. Herein, we developed a novel polymeric nanoparticle (NP delivery system based on vitamin E modified aliphatic polycarbonate (mPEG-PCC-VE to facilitate oral absorption of OA. OA encapsulated mPEG-PCC-VE NPs (OA/mPEG-PCC-VE NPs showed uniform particle size of about 170 nm with high drug loading capability (8.9%. Furthermore, the polymeric mPEG-PCC-VE NPs, with good colloidal stability and pH-sensitive drug release characteristics, significantly enhanced the in vitro dissolution of OA in the alkaline medium. The in situ single pass intestinal perfusion (SPIP studies performed on rats demonstrated that the OA/mPEG-PCC-VE NPs showed significantly improved permeability in the whole intestinal tract when compared to OA solution, especially for duodenum and colon. As a result, the in vivo pharmacokinetics study indicated that the bioavailability of OA/mPEG-PCC-VE NPs showed 1.5-fold higher than commercially available OA tablets. These results suggest that mPEG-PCC-VE NPs are a promising platform to facilitate the oral delivery of OA.

A stable isotope approach for source apportionment of chlorinated ethene plumes at a complex multi-contamination events urban site

Science.gov (United States)

Nijenhuis, Ivonne; Schmidt, Marie; Pellegatti, Eleonora; Paramatti, Enrico; Richnow, Hans Hermann; Gargini, Alessandro

2013-10-01

The stable carbon isotope composition of chlorinated aliphatic compounds such as chlorinated methanes, ethanes and ethenes was examined as an intrinsic fingerprint for apportionment of sources. A complex field site located in Ferrara (Italy), with more than 50 years history of use of chlorinated aliphatic compounds, was investigated in order to assess contamination sources. Several contamination plumes were found in a complex alluvial sandy multi-aquifer system close to the river Po; sources are represented by uncontained former industrial and municipal dump sites as well as by spills at industrial areas. The carbon stable isotope signature allowed distinguishing 2 major sources of contaminants. One source of chlorinated aliphatic contaminants was strongly depleted in 13C (-40‰ which is commonly observed in recent production of chlorinated solvents. The degradation processes in the plumes could be traced interpreting the isotope enrichment and depletion of parent and daughter compounds, respectively. We demonstrate that, under specific production conditions, namely when highly chlorinated ethenes are produced as by-product during chloromethanes production, 13C depleted fingerprinting of contaminants can be obtained and this can be used to track sources and address the responsible party of the pollution in urban areas.

Elaboration of modified poly(NiII-DHS films as electrodes by the electropolymerization of Ni(II-[5,5′-dihydroxysalen] onto indium tin oxide surface and study of their electrocatalytic behavior toward aliphatic alcohols

Directory of Open Access Journals (Sweden)

Ali Ourari

2017-11-01

Full Text Available Nickel(II-DHS complex was obtained from N,N′-bis(2,5-dihydroxybenzylidene-1,2-diaminoethane (H2DHS ligand and nickel acetate tetrahydrated in ethanolic solution with stirring under reflux. This complex, dissolved in an alkaline solution, was oxidized to form electroactive films strongly adhered on the ITO (indium tin oxide electrode surface. In this alkaline solution, the poly-[NiII-DHS]/ITO films showed the typical voltammetric response of (Ni2+/Ni3+ redox couple centers which are immobilized in the polymer-film. The modified electrodes (MEs obtained were also characterized by several techniques such as scanning electronic microscopy, atomic force microscopy and electrochemical methods. The electrocatalytic behavior of these MEs toward the oxidation reaction of some aliphatic alcohols such as methanol, ethanol, 2-Methyl-1-propanol and isopropanol was investigated. The voltammograms recorded with these alcohols showed good electrocatalytic efficiency. The electrocatalytic currents were at least 80 times higher than those obtained for the oxidation of methanol on electrodes modified with nickel hydroxide films in alkaline solutions. We noticed that these electrocatalytic currents are proportional to the concentration of methanol (0.050–0.30 μM. In contrast, those recorded for the oxidation of other aliphatic short chain alcohols such as ethanol, 2-methyl-1-propanol and isopropanol are rather moderately weaker. In all cases the electrocatalytic currents presented a linear dependence with the concentration of alcohol. These modified electrodes could be applied as alcohol sensors.

Measurements of activity coefficients at infinite dilution of aromatic and aliphatic hydrocarbons, alcohols, and water in the new ionic liquid [EMIM][SCN] using GLC

International Nuclear Information System (INIS)

Domanska, Urszula; Marciniak, Andrzej

2008-01-01

A new ionic liquid was chosen for the separation of aromatic hydrocarbons from aliphatic hydrocarbons. The activity coefficients at infinite dilution, γ 13 ∞ for 29 solutes: alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, and water in the ionic liquid 1-ethyl-3-methyl-imidazolium thiocyanate [EMIM][SCN] were determined by gas-liquid chromatography at the temperatures from 298.15 K to 368.15 K. The values of the partial molar excess enthalpies at infinite dilution ΔH 1 E,∞ were calculated from the experimental γ 13 ∞ values obtained over the temperature range. The selectivities for the hexane/benzene and cyclohexane/benzene separation problems were calculated from the γ 13 ∞ and compared to the other ionic liquids, NMP and sulfolane, taken from the recent literature. This work demonstrates that with chosen ionic liquid it is possible to separate different organic compounds with the highest selectivity ever published

EFSA Panel on F ood Contact Materials, Enzymes, Flavourings and Processing Aids (CEF) ; Scientific Opinion on Flavouring Group Evaluation 63, Revision 2 (FGE.63Rev2): Consideration of aliphatic secondary alcohols, ketones and related esters evaluated by JECFA (59 th and 6 9 th meeting s

DEFF Research Database (Denmark)

Beltoft, Vibe Meister; Binderup, Mona-Lise; Frandsen, Henrik Lauritz

evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of 20 aliphatic secondary alcohols, ketones and related esters evaluated by the JECFA at the 59th and 69th meetings in 2002 and 2008. This revision is made due to inclusion of one...

Deuterium magnetic resonance of some polymorphic liquid crystals: The conformation of the aliphatic end chains

International Nuclear Information System (INIS)

Hsi, S.; Zimmermann, H.; Luz, Z.

1978-01-01

Deuterium magnetic resonance measurements of four members of the homologous series p-alkoxybenzylidene-p-alkylaniline (noxm), perdeuterated in their alkoxy chains, are reported. The compounds studied were 40x7, 50x7, 60x7, and 70x7. For 50x7 various isotopic species specifically deuterated in the alkoxy chains, as well as in the benzylidine moiety, were prepared and their DMR studied. These measurements allowed a complete assignment of the resonances from the alkoxy chain. The spectrum of all four compounds was studied over their whole mesomorphic regions. In most phases well resolved spectra were obtained yielding the various quadrupole splittings and in many cases also the dipolar interactions within the methylene and methyl groups. Using double quantum spectroscopy dipolar splitting between different methylene deuterons could also be resolved. The methylene quadrupolar splittings and the dipolar interaction within the methylene groups decrease along the chain towards the methyl end in a characteristic stepwise manner. This behavior is attributed to chain reorientational freedom and is quantitatively interpreted in terms of two structural factors: (i) Fast dynamical equilibrium between the all-trans conformation of the alkoxy chains and chain conformations involving one or more kinks, and (ii) a molecular model in which the aliphatic chain axis is inclined with respect to the molecular long axis. The characteristic pattern of the splitting can then be reproduced by assuming a monotonically increasing kink probabilities along the chain towards its methyl end. This interpretation is used to estimate the kink probability distribution in the alkoxy chains in the various compounds and mesophases. No significant effect of the mesophase structure on the kink statistics was found

Presence of aliphatic and polycyclic aromatic hydrocarbons in near-surface sediments of an oil spill area in Bohai Sea.

Science.gov (United States)

Li, Shuanglin; Zhang, Shengyin; Dong, Heping; Zhao, Qingfang; Cao, Chunhui

2015-11-15

In order to determine the source of organic matter and the fingerprint of the oil components, 50 samples collected from the near-surface sediments of the oil spill area in Bohai Sea, China, were analyzed for grain size, total organic carbon, aliphatic hydrocarbons (AHs), and polycyclic aromatic hydrocarbons (PAHs). The concentrations of C15-35 n-alkanes and 16 United States Environmental Protection Agency (US EPA) priority pollutant PAHs were found in the ranges of 0.88-3.48μg g(-1) and 9.97-490.13ng/g, respectively. The terrestrial organic matters characterized by C27-C35 n-alkanes and PAHs, resulting from the combustion of higher plants, are dominantly contributed from the transportation of these plants by rivers. Marine organic matters produced from plankton and aquatic plants were represented by C17-C26 n-alkanes in AHs. Crude oil, characterized by C17-C21 n-alkanes, unresolved complex mixture (UCM) with a mean response factor of C19 n-alkanes, low levels of perylene, and a high InP/(InP+BghiP) ratio, seeped into the oceans from deep hydrocarbon reservoirs, as a result of geological faults. Copyright © 2015 Elsevier Ltd. All rights reserved.

Novel synthetic approach to asymmetric monocationic trimethine cyanine dyes derived from N-ethyl quinolinum moiety. Combined fluorescent and ICD probes for AT-DNA labelling

Energy Technology Data Exchange (ETDEWEB)

Kurutos, Atanas [Department of Pharmaceutical and Applied Organic Chemistry, Faculty of Chemistry, University of Sofia, 1164 Sofia (Bulgaria); Crnolatac, Ivo; Orehovec, Iva [Laboratory for Study of Interactions of Biomacromolecules, Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb (Croatia); Gadjev, Nikolai [Department of Pharmaceutical and Applied Organic Chemistry, Faculty of Chemistry, University of Sofia, 1164 Sofia (Bulgaria); Piantanida, Ivo, E-mail: pianta@irb.hr [Laboratory for Study of Interactions of Biomacromolecules, Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička c. 54, 10000 Zagreb (Croatia); Deligeorgiev, Todor, E-mail: ohtak@chem.uni-sofia.bg [Department of Pharmaceutical and Applied Organic Chemistry, Faculty of Chemistry, University of Sofia, 1164 Sofia (Bulgaria)

2016-06-15

Two asymmetric monocationic trimethine cyanine dyes were obtained via condensation reaction between 2-methylbenzothialolium salts containing various (aliphatic and benzyl) substituents on the nitrogen atom of the benzothiazolic chromophore, and 1-ethyl−4-(2-(phenylamine)vinyl)quinolin−1-ium iodide, by a novel improved method at room temperature under mild conditions. Both compounds bind non-covalently to double stranded DNA and RNA by micromolar affinity, but give highly selective fluorescent response>650 nm for only AT-DNA sequences at excess of DNA over dye, combined with equally AT-DNA selective ICD response at dye/DNA crowded conditions (r{sub [dye]/[AT-DNA]}>0.2)-namely ICD bands (attributed to dye-dimer formation) allow determination of AT-DNA at submicromolar concentrations. Selectivity was attributed to particular steric properties of AT-DNA minor groove in respect to other studied ds-DNA/RNA. Comparison of aliphatic- and benzyl- dye showed that only aliphatic- derivative revealed ICD band upon binding to AU-RNA major groove and short AT-sequences in mixed sequence (ct-)DNA.

Quantum chemical analysis of thermodynamics of 2D cluster formation of alkanes at the water/vapor interface in the presence of aliphatic alcohols.

Science.gov (United States)

Vysotsky, Yu B; Kartashynska, E S; Belyaeva, E A; Fainerman, V B; Vollhardt, D; Miller, R

2015-11-21

Using the quantum chemical semi-empirical PM3 method it is shown that aliphatic alcohols favor the spontaneous clusterization of vaporous alkanes at the water surface due to the change of adsorption from the barrier to non-barrier mechanism. A theoretical model of the non-barrier mechanism for monolayer formation is developed. In the framework of this model alcohols (or any other surfactants) act as 'floats', which interact with alkane molecules of the vapor phase using their hydrophobic part, whereas the hydrophilic part is immersed into the water phase. This results in a significant increase of contact effectiveness of alkanes with the interface during the adsorption and film formation. The obtained results are in good agreement with the existing experimental data. To test the model the thermodynamic and structural parameters of formation and clusterization are calculated for vaporous alkanes C(n)H(2n+2) (n(CH3) = 6-16) at the water surface in the presence of aliphatic alcohols C(n)H(2n+1)OH (n(OH) = 8-16) at 298 K. It is shown that the values of clusterization enthalpy, entropy and Gibbs' energy per one monomer of the cluster depend on the chain lengths of corresponding alcohols and alkanes, the alcohol molar fraction in the monolayers formed, and the shift of the alkane molecules with respect to the alcohol molecules Δn. Two possible competitive structures of mixed 2D film alkane-alcohol are considered: 2D films 1 with single alcohol molecules enclosed by alkane molecules (the alcohols do not form domains) and 2D films 2 that contain alcohol domains enclosed by alkane molecules. The formation of the alkane films of the first type is nearly independent of the surfactant type present at the interface, but depends on their molar fraction in the monolayer formed and the chain length of the compounds participating in the clusterization, whereas for the formation of the films of the second type the interaction between the hydrophilic parts of the surfactant is

Ion-exclusion chromatography with conductimetric detection of aliphatic carboxylic acids on a weakly acidic cation-exchange resin by elution with benzoic acid-beta-cyclodextrin.

Science.gov (United States)

Tanaka, Kazuhiko; Mori, Masanobu; Xu, Qun; Helaleh, Murad I H; Ikedo, Mikaru; Taoda, Hiroshi; Hu, Wenzhi; Hasebe, Kiyoshi; Fritz, James S; Haddad, Paul R

2003-05-16

In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression.

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

OpenAIRE

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

2013-01-01

Chemical group 1 (CG 1) consists of straight-chain primary aliphatic alcohols/aldehydes/acids, acetals and esters with esters containing saturated alcohols and acetals containing saturated aldehydes of which 86 are currently authorised for use as flavours in food. The FEEDAP Panel was unable to perform an assessment of ethyl oleate because of its insufficient purity. The following compounds are considered to be safe for all animal species at the use level proposed for feed flavourings: formic...

Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots

Science.gov (United States)

Powell, C. L.; Goltz, M. N.; Agrawal, A.

2014-12-01

Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~ 1.9 mg L- 1, and initial aqueous [CAH] ~ 150 μg L- 1; cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12 ± 0.01 and 0.59 ± 0.07 d- 1, respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

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

Energy Technology Data Exchange (ETDEWEB)

Evans, A. Jr.; Zelazny, L.W. (Virginia Polytechnic Institute and State Univ., Blacksburg (USA))

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.

Extraction of toluene from aliphatic compounds using an ionic liquid as solvent: Influence of the alkane on the (liquid + liquid) equilibrium

International Nuclear Information System (INIS)

Gonzalez, Emilio J.; Calvar, Noelia; Dominguez, Irene; Dominguez, Angeles

2011-01-01

Research highlights: → An ionic liquid was analyzed as solvent for extraction of toluene from alkanes. → Liquid-liquid equilibrium data were measured at 298.15 K and atmospheric pressure. → Selectivity and solute distribution ratio were obtained and compared with literature. → The Othmer-Tobias equation was used to ascertain the experimental LLE data. → Experimental data were correlated using NRTL and UNIQUAC models. - Abstract: In this paper, the feasibility of using 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid, [EMim][ESO 4 ], as solvent for the extraction of toluene from aliphatic compounds (hexane, heptane, octane, or nonane) was analyzed. (Liquid + liquid) equilibrium (LLE) data for the ternary systems {alkane (1) + toluene (2) + [EMim][ESO 4 ] (3)} were measured at T = 298.15 K and atmospheric pressure. Selectivity and solute distribution ratio were calculated from the experimental LLE data, and the obtained values were compared to those previously reported using other ionic liquids and sulfolane. The degree of consistency of the experimental LLE data was ascertained using the Othmer-Tobias equation. Finally, the experimental LLE data were satisfactorily correlated with NRTL and UNIQUAC models.

Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state 13C NMR and solution 31P NMR spectroscopy

Science.gov (United States)

LIU, S. S.; Zhu, Y.; Meng, W.; Wu, F.

2016-12-01

Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state 13C NMR and solution 31P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O-C-O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH3 and COO/N-C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH3 and COO/N-C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes.

Swift heavy ion induced modification of aliphatic polymers

Energy Technology Data Exchange (ETDEWEB)

Hossain, Umme Habiba

2015-01-15

In this thesis, the high energy heavy ion induced modification of aliphatic polymers is studied. Two polymer groups, namely polyvinyl polymers (PVF, PVAc, PVA and PMMA) and fluoropolymers (PVDF, ETFE, PFA and FEP) were used in this work. Polyvinyl polymers were investigated since they will be used as insulating materials in the superconducting magnets of the new ion accelerators of the planned International Facility for Antiproton and Ion Research (FAIR) at the GSI Helmholtz-Centre of Heavy Ion Research (GSI) in Darmstadt. In order to study ion-beam induced degradation, all polymer foils were irradiated at the GSI linear accelerator UNILAC using several projectiles (U, Au, Sm, Xe) and experimentation sites (beam lines X0 and M3) over a large fluence regime (1 x 10{sup 10} - 5 x 10{sup 12} ions/cm{sup 2}). Five independent techniques, namely infrared (FT-IR) and ultraviolet-visible (UV-Vis) spectroscopy, residual gas analysis (RGA), thermal gravimetric analysis (TGA), and mass loss analysis (ML), were used to analyze the irradiated samples. FT-IR spectroscopy revealed that ion irradiation led to the decrease of characteristic band intensities showing the general degradation of the polymers, with scission of side groups and the main backbone. As a consequence of the structural modification, new bands appeared. UV-Vis transmission analysis showed an absorption edge shift from the ultraviolet region towards the visible region indicating double bond and conjugated double bond formation. On-line massspectrometric residual gas analysis showed the release of small gaseous fragment molecules. TGA analysis gave evidence of a changed thermal stability. With ML analysis, the considerable mass loss was quantified. The results of the five complementary analytical methods show how heavy ion irradiation changes the molecular structure of the polymers. Molecular degradation mechanisms are postulated. The amount of radiation damage is found to be sensitive to the used type of ionic

Pro-toxic 1,2-Dehydropyrrolizidine alkaloid esters, including unprecedented 10-membered macrocyclic diesters, in the medicinally-used Alafia cf. caudata and Amphineurion marginatum (Apocynaceae: Apocynoideae: Nerieae and Apoc

Science.gov (United States)

The attraction of pyrrolizidine alkaloid-pharmacophagous insects indicated the presence of pro-toxic dehydropyrrolizidine alkaloids in Alafia cf. caudata Stapf (Nerieae: Alafinae) and Amphineurion marginatum (Roxb.) D.J. Middleton (Apocyneae: Amphineuriinae). Subsequently, monoesters of retronecine ...

Determining the thickness of aliphatic alcohol monolayers covalently attached to silicon oxide surfaces using angle-resolved X-ray photoelectron spectroscopy

Science.gov (United States)

Lee, Austin W. H.; Kim, Dongho; Gates, Byron D.

2018-04-01

The thickness of alcohol based monolayers on silicon oxide surfaces were investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS). Advantages of using alcohols as building blocks for the formation of monolayers include their widespread availability, ease of handling, and stability against side reactions. Recent progress in microwave assisted reactions demonstrated the ease of forming uniform monolayers with alcohol based reagents. The studies shown herein provide a detailed investigation of the thickness of monolayers prepared from a series of aliphatic alcohols of different chain lengths. Monolayers of 1-butanol, 1-hexanol, 1-octanol, 1-decanol, and 1-dodecanol were each successfully formed through microwave assisted reactions and characterized by ARXPS techniques. The thickness of these monolayers consistently increased by ∼1.0 Å for every additional methylene (CH2) within the hydrocarbon chain of the reagents. Tilt angles of the molecules covalently attached to silicon oxide surfaces were estimated to be ∼35° for each type of reagent. These results were consistent with the observations reported for thiol based or silane based monolayers on either gold or silicon oxide surfaces, respectively. The results of this study also suggest that the alcohol based monolayers are uniform at a molecular level.

Molecular Connectivity Predefines Polypharmacology: Aliphatic Rings, Chirality, and sp3 Centers Enhance Target Selectivity

Directory of Open Access Journals (Sweden)

Stefania Monteleone

2017-08-01

Full Text Available Dark chemical matter compounds are small molecules that have been recently identified as highly potent and selective hits. For this reason, they constitute a promising class of possible candidates in the process of drug discovery and raise the interest of the scientific community. To this purpose, Wassermann et al. (2015 have described the application of 2D descriptors to characterize dark chemical matter. However, their definition was based on the number of reported positive assays rather than the number of known targets. As there might be multiple assays for one single target, the number of assays does not fully describe target selectivity. Here, we propose an alternative classification of active molecules that is based on the number of known targets. We cluster molecules in four classes: black, gray, and white compounds are active on one, two to four, and more than four targets respectively, whilst inactive compounds are found to be inactive in the considered assays. In this study, black and inactive compounds are found to have not only higher solubility, but also a higher number of chiral centers, sp3 carbon atoms and aliphatic rings. On the contrary, white compounds contain a higher number of double bonds and fused aromatic rings. Therefore, the design of a screening compound library should consider these molecular properties in order to achieve target selectivity or polypharmacology. Furthermore, analysis of four main target classes (GPCRs, kinases, proteases, and ion channels shows that GPCR ligands are more selective than the other classes, as the number of black compounds is higher in this target superfamily. On the other side, ligands that hit kinases, proteases, and ion channels bind to GPCRs more likely than to other target classes. Consequently, depending on the target protein family, appropriate screening libraries can be designed in order to minimize the likelihood of unwanted side effects early in the drug discovery process

Diketones and ketoesters synthesis by acylation of substituted trimethylsilyl lithio-malonates

International Nuclear Information System (INIS)

Mayani, Mbutyabo

1983-01-01

The acylation of trimethylsilyl substituted lithio malonates with dicarbonyl-dichlorides and diacid monoester chlorides gives, after a simple hydrolysis by water, various diketones and ketoesters. The yields are generally good. The method is easy. (author) [fr

Poly(malachite green) at nafion doped multi-walled carbon nanotube composite film for simple aliphatic alcohols sensor.

Science.gov (United States)

Umasankar, Yogeswaran; Periasamy, Arun Prakash; Chen, Shen-Ming

2010-01-15

Conductive composite film which contains nafion (NF) doped multi-walled carbon nanotubes (MWCNTs) along with the incorporation of poly(malachite green) (PMG) has been synthesized on glassy carbon electrode (GCE), gold and indium tin oxide (ITO) electrodes by potentiostatic methods. The presence of MWCNTs in the composite film (MWCNTs-NF-PMG) enhances surface coverage concentration (Gamma) of PMG to approximately 396%, and increases the electron transfer rate constant (k(s)) to approximately 305%. Similarly, electrochemical quartz crystal microbalance study reveals the enhancement in the deposition of PMG at MWCNTs-NF film. The surface morphology of the composite film deposited on ITO electrode has been studied using scanning electron microscopy (SEM) and scanning tunneling microscopy (STM). These two techniques reveal that the PMG incorporated on MWCNTs-NF film. The MWCNTs-NF-PMG composite film also exhibits promising enhanced electrocatalytic activity towards the simple aliphatic alcohols such as methanol, ethanol and propanol. The electroanalytical responses of analytes at NF-PMG and MWCNTs-NF-PMG films were measured using both cyclic voltammetry (CV) and differential pulse voltammetry (DPV). From electroanalytical studies, well defined voltammetric peaks have been obtained at MWCNTs-NF-PMG composite film for methanol, ethanol and propanol at Epa=609, 614 and 602mV respectively. The sensitivity of MWCNTs-NF-PMG composite film towards methanol, ethanol and propanol in CV technique are 0.59, 0.36 and 0.92microAmM(-1)cm(-2) respectively, which are higher than NF-PMG film. Further, the sensitivity values obtained using DPV are higher than the values obtained using CV technique.

Substrate-Triggered Formation and Remarkable Stability of the C-H-Cleaving Chloroferryl Intermediate in the Aliphatic Halogenase, SyrB2†

Science.gov (United States)

Matthews, Megan L.; Krest, Courtney M.; Barr, Eric W.; Vaillancourt, Frédéric H.; Walsh, Christopher T.; Green, Michael T.; Krebs, Carsten; Bollinger, J. Martin

2009-01-01

Aliphatic halogenases activate O2, cleave α-ketoglutarate (αKG) to CO2 and succinate, and form haloferryl [X-Fe(IV)=O; X = Cl, Br] complexes that cleave aliphatic C-H bonds to install halogens during the biosynthesis of natural products by non-ribosomal peptide synthetases (NRPSs). For the related αKG-dependent dioxygenases, it has been shown that reaction of the Fe(II) cofactor with O2 to form the C-H-cleaving ferryl complex is “triggered” by binding of the target substrate. In this study, we have tested for and defined structural determinants of substrate triggering (ST) in the halogenase, SyrB2, from the syringomycin E biosynthetic NRPS of Pseudomonas syringae B301D. As for other halogen ases, the substrate of SyrB2 is complex, consisting of l-Thr tethered via thioester linkage to a covalently bound phosphopantetheine (PPant) cofactor of a carrier protein, SyrB1. Without an appended amino acid, SyrB1 does not trigger formation of the chloroferryl intermediate state in SyrB2, even in the presence of free l-Thr or its analogues, but SyrB1 charged either by l-Thr or by any of several non-native amino acids does trigger the reaction by as much as 8,000-fold (for l-Thr-S-SyrB1). Triggering efficacy is sensitive to the structures of both the amino acid and the carrier protein, being diminished by 5–20-fold when the native l-Thr is replaced by another amino acid and by ∼ 40-fold when SyrB1 is replaced by a heterologous carrier protein, CytC2. The directing effect of the carrier protein and consequent tolerance for profound modifications to the target amino acid allow the chloroferryl state to be formed in the presence of substrates that perturb the ratio of its two putative coordination isomers, lack the target C-H bond (l-Ala-S-SyrB1), or contain a C-H bond of enhanced strength (l-cyclopropylglycyl-S-SyrB1). For the latter two cases, the SyrB2 chloroferryl state so formed exhibits unprecedented stability (t1/2 = 30 – 110 min at 0 °C), can be trapped in

Toxicological and industrial-medical aspects of exposure to dichloromethane and other aliphatic halocarbons; Toxikologische und arbeitsmedizinische Aspekte der Exposition gegenueber Dichlormethan und anderen aliphatischen Halogenkohlenwasserstoffen

Energy Technology Data Exchange (ETDEWEB)

Pankow, D. [ed.] [Halle-Wittenberg Univ., Halle (Germany). Inst. fuer Pharmakologie und Toxikologie; Verkoyen, C. [ed.] [Deutsche Forschungsanstalt fuer Luft- und Raumfahrt e.V. (DLR), Bonn (Germany). Projekttraegerschaften fuer Arbeit, Umwelt und Gesundheit; Wolna, P. [ed.] [Halle-Wittenberg Univ., Halle (Germany). Inst. fuer Pharmakologie und Toxikologie; Wuenscher, U. [ed.] [Halle-Wittenberg Univ., Halle (Germany). Inst. fuer Pharmakologie und Toxikologie

1993-12-31

The present volume is based on contributions to the workshop on ``Toxicological and industrial-medical aspects of exposure to dichloromethane and other aliphatic halocarbons`` which took place in Halle (Saale) on 25 November 1993. The purpose of the master project was to examine by animal experiment the effects of certain noxions factors on moderate CO hypoxia and the cardiovascular system as a whole following DCM intoxication, in particular the additional uptake of solvents and drings. Another part of the project consisted in specific examinations of gene toxicity. (orig./MG) [Deutsch] Der vorliegende Berichtsband entstand aus Beitraegen eines am 25. November 1993 in Halle (Saale) stattgefundenen Workshops ``Toxikologische und arbeitsmedizinische Aspekte der Exposition gegenueber Dichlormethan und anderen aliphatischen Halogenkohlenwasserstoffen``. Das Ziel des Vorhabens bestand darin, tierexperimentell die Beeinflussung der moderaten CO-Hypoxie nach DCM-Aufnahme durch verschiedene Faktoren, insbesondere durch zusaetzliche Aufnahme von Loesungs- und Arzneimitteln zu untersuchen sowie Wirkungen auf das Herz-Kreislauf-System zu erfassen. Weiterhin erfolgten gezielte Untersuchungen zur Gentoxizitaet. (orig./MG)

Matrix-assisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers using new ionic liquid matrices.

Science.gov (United States)

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. Copyright © 2011 John Wiley & Sons, Ltd.

Study of the electron beam irradiation effect on some properties of aromatic aliphatic copolyester films; Estudo do efeito da radiacao por feixe de eletrons nas propriedades de filmes de copoliester alifatico aromatico

Energy Technology Data Exchange (ETDEWEB)

Poveda, Patricia Negrini Siqueira

2008-07-01

Biodegradable and green plastics are the new tendency in the world. The effect of the electron beam irradiation in aromatic aliphatic copolyester and the blend with corn starch films (Ecoflex{sup R} and Ecobras{sup R}) were studied by tensile strength at break, elongation at break, Scanning Electronic Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), Differential Scanning Calorimetry (DSC), crosslinking degree and biodegradability. The measurements in both, the machine direction and the transverse direction were made for mechanical tests. It was found that, the electron irradiation caused an increase in the strength at break of the blend with corn starch film, when doses of up to 10 kGy were applied. A significant decrease of the elongation at break of the blend with corn starch was observed at doses of 10 kGy and 40 kGy. It was not found important change in tensile properties for aromatic aliphatic copolyester. Structural changes of the samples (crosslinking or degradation) by SEM were not observed. The FT-IR identified the characteristic peaks of each involved functional group (copolyester and corn starch). However, it was not found bands of oxidation of the samples. In the DSC, changes in the melting temperature of the irradiated Ecoflex{sup R} and Ecobras{sup R} samples, was not identified when compared with the samples of reference. However, it was verified a reduction in the melting enthalpy of the Ecobras{sup R} samples after irradiation. The Ecobras{sup R} material presented crosslinking, when submitted to doses of 10 kGy and 40 kGy. The Ecoflex{sup R} material did not present crosslinking when submitted to these doses. The biodegradability of the materials was evaluated by two methods of test: soil simulated and enzymatic. In both methods, the irradiated samples presented faster biodegradation than the references not irradiated. (author)

Factor VII and protein C are phosphatidic acid-binding proteins.

Science.gov (United States)

Tavoosi, Narjes; Smith, Stephanie A; Davis-Harrison, Rebecca L; Morrissey, James H

2013-08-20

Seven proteins in the human blood clotting cascade bind, via their GLA (γ-carboxyglutamate-rich) domains, to membranes containing exposed phosphatidylserine (PS), although with membrane binding affinities that vary by 3 orders of magnitude. Here we employed nanodiscs of defined phospholipid composition to quantify the phospholipid binding specificities of these seven clotting proteins. All bound preferentially to nanobilayers in which PS headgroups contained l-serine versus d-serine. Surprisingly, however, nanobilayers containing phosphatidic acid (PA) bound substantially more of two of these proteins, factor VIIa and activated protein C, than did equivalent bilayers containing PS. Consistent with this finding, liposomes containing PA supported higher proteolytic activity by factor VIIa and activated protein C toward their natural substrates (factors X and Va, respectively) than did PS-containing liposomes. Moreover, treating activated human platelets with phospholipase D enhanced the rates of factor X activation by factor VIIa in the presence of soluble tissue factor. We hypothesize that factor VII and protein C bind preferentially to the monoester phosphate of PA because of its accessibility and higher negative charge compared with the diester phosphates of most other phospholipids. We further found that phosphatidylinositol 4-phosphate, which contains a monoester phosphate attached to its myo-inositol headgroup, also supported enhanced enzymatic activity of factor VIIa and activated protein C. We conclude that factor VII and protein C bind preferentially to monoester phosphates, which may have implications for the function of these proteases in vivo.

Phthalates Are Metabolised by Primary Thyroid Cell Cultures but Have Limited Influence on Selected Thyroid Cell Functions In Vitro.

Directory of Open Access Journals (Sweden)

Juliana Frohnert Hansen

Full Text Available Phthalates are plasticisers added to a wide variety of products, resulting in measurable exposure of humans. They are suspected to disrupt the thyroid axis as epidemiological studies suggest an influence on the peripheral thyroid hormone concentration. The mechanism is still unknown as only few in vitro studies within this area exist. The aim of the present study was to investigate the influence of three phthalate diesters (di-ethyl phthalate, di-n-butyl phthalate (DnBP, di-(2-ethylhexyl phthalate (DEHP and two monoesters (mono-n-butyl phthalate and mono-(2-ethylhexyl phthalate (MEHP on the differentiated function of primary human thyroid cell cultures. Also, the kinetics of phthalate metabolism were investigated. DEHP and its monoester, MEHP, both had an inhibitory influence on 3'-5'-cyclic adenosine monophosphate secretion from the cells, and MEHP also on thyroglobulin (Tg secretion from the cells. Results of the lactate dehydrogenase-measurements indicated that the MEHP-mediated influence was caused by cell death. No influence on gene expression of thyroid specific genes (Tg, thyroid peroxidase, sodium iodine symporter and thyroid stimulating hormone receptor by any of the investigated diesters could be demonstrated. All phthalate diesters were metabolised to the respective monoester, however with a fall in efficiency for high concentrations of the larger diesters DnBP and DEHP. In conclusion, human thyroid cells were able to metabolise phthalates but this phthalate-exposure did not appear to substantially influence selected functions of these cells.

Influence of phthalates on in vitro innate and adaptive immune responses.

Directory of Open Access Journals (Sweden)

Juliana Frohnert Hansen

Full Text Available Phthalates are a group of endocrine disrupting chemicals, suspected to influence the immune system. The aim of this study was to investigate the influence of phthalates on cytokine secretion from human peripheral blood mononuclear cells. Escherichia coli lipopolysaccharide and phytohemagglutinin-P were used for stimulation of monocytes/macrophages and T cells, respectively. Cells were exposed for 20 to 22 hours to either di-ethyl, di-n-butyl or mono-n-butyl phthalate at two different concentrations. Both diesters were metabolised to their respective monoester and influenced cytokine secretion from both monocytes/macrophages and T cells in a similar pattern: the secretion of interleukin (IL-6, IL-10 and the chemokine CXCL8 by monocytes/macrophages was enhanced, while tumour necrosis factor (TNF-α secretion by monocytes/macrophages was impaired, as was the secretion of IL-2 and IL-4, TNF-α and interferon-γ by T cells. The investigated phthalate monoester also influenced cytokine secretion from monocytes/macrophages similar to that of the diesters. In T cells, however, the effect of the monoester was different compared to the diesters. The influence of the phthalates on the cytokine secretion did not seem to be a result of cell death. Thus, results indicate that both human innate and adaptive immunity is influenced in vitro by phthalates, and that phthalates therefore may affect cell differentiation and regenerative and inflammatory processes in vivo.

Human breast milk contamination with phthalates and alterations of endogenous reproductive hormones in infants three months of age

DEFF Research Database (Denmark)

Main, Katharina M; Mortensen, Gerda Krog; Kaleva, Marko M

2006-01-01

Phthalates adversely affect the male reproductive system in animals. We investigated whether phthalate monoester contamination of human breast milk had any influence on the postnatal surge of reproductive hormones in newborn boys as a sign of testicular dysgenesis....

Metabolism of phthalates in humans

DEFF Research Database (Denmark)

Frederiksen, Hanne; Skakkebaek, Niels E; Andersson, Anna-Maria

2007-01-01

on the foetal testis and they are similar to those seen in humans with testicular dysgenesis syndrome. Therefore, exposure of the human foetus and infants to phthalates via maternal exposure is a matter of concern. The metabolic pathways of phthalate metabolites excreted in human urine are partly known for some...... phthalates, but our knowledge about metabolic distribution in the body and other biological fluids, including breast milk, is limited. Compared to urine, human breast milk contains relatively more of the hydrophobic phthalates, such as di-n-butyl phthalate and the longer-branched, di(2-ethylhexyl) phthalate...... (DEHP) and di-iso-nonyl phthalate (DiNP); and their monoester metabolites. Urine, however, contains relatively more of the secondary metabolites of DEHP and DiNP, as well as the monoester phthalates of the more short-branched phthalates. This differential distribution is of special concern as...

Phthalates Are Metabolised by Primary Thyroid Cell Cultures but Have Limited Influence on Selected Thyroid Cell Functions In Vitro

DEFF Research Database (Denmark)

Hansen, Juliana Frohnert; Brorson, Marianne Møller; Boas, Malene

2016-01-01

Phthalates are plasticisers added to a wide variety of products, resulting in measurable exposure of humans. They are suspected to disrupt the thyroid axis as epidemiological studies suggest an influence on the peripheral thyroid hormone concentration. The mechanism is still unknown as only few...... in vitro studies within this area exist. The aim of the present study was to investigate the influence of three phthalate diesters (di-ethyl phthalate, di-n-butyl phthalate (DnBP), di-(2-ethylhexyl) phthalate (DEHP)) and two monoesters (mono-n-butyl phthalate and mono-(2-ethylhexyl) phthalate (MEHP......)) on the differentiated function of primary human thyroid cell cultures. Also, the kinetics of phthalate metabolism were investigated. DEHP and its monoester, MEHP, both had an inhibitory influence on 3'-5'-cyclic adenosine monophosphate secretion from the cells, and MEHP also on thyroglobulin (Tg) secretion from...

Highly phosphorylated functionalized rice starch produced by transgenic rice expressing the potato GWD1 gene

DEFF Research Database (Denmark)

Chen, Yaling; Sun, Xiao-Feng; Zhou, Xin

2017-01-01

Starch phosphorylation occurs naturally during starch metabolism in the plant and is catalysed by glucan water dikinases (GWD1) and phosphoglucan water dikinase/glucan water dikinase 3 (PWD/GWD3). We generated six stable individual transgenic lines by over-expressing the potato GWD1 in rice....... Transgenic rice grain starch had 9-fold higher 6-phospho (6-P) monoesters and double amounts of 3-phospho (3-P) monoesters, respectively, compared to control grain. The shape and topography of the transgenic starch granules were moderately altered including surface pores and less well defined edges...... content was positively correlated with short chains of DP6-12. The starch pasting temperature, peak viscosity and the breakdown were lower but the setback was higher for transgenic rice flour. The 6-P content was negatively correlated with texture adhesiveness but positively correlated...

Highly phosphorylated functionalized rice starch produced by transgenic rice expressing the potato GWD1 gene

DEFF Research Database (Denmark)

Chen, Yaling; Sun, Xiao; Zhou, Xin Mao

2017-01-01

Starch phosphorylation occurs naturally during starch metabolism in the plant and is catalysed by glucan water dikinases (GWD1) and phosphoglucan water dikinase/glucan water dikinase 3 (PWD/GWD3). We generated six stable individual transgenic lines by over-expressing the potato GWD1 in rice....... Transgenic rice grain starch had 9-fold higher 6-phospho (6-P) monoesters and double amounts of 3-phospho (3-P) monoesters, respectively, compared to control grain. The shape and topography of the transgenic starch granules were moderately altered including surface pores and less well defined edges....... The gelatinization temperatures of both rice flour and extracted starch were significantly lower than those of the control and hence negatively correlated with the starch phosphate content. The 6-P content was positively correlated with amylose content and relatively long amylopectin chains with DP25-36, and the 3-P...

Use of aliphatic n-alkynes to discriminate soil nitrification activities of ammonia-oxidizing thaumarchaea and bacteria.

Science.gov (United States)

Taylor, Anne E; Vajrala, Neeraja; Giguere, Andrew T; Gitelman, Alix I; Arp, Daniel J; Myrold, David D; Sayavedra-Soto, Luis; Bottomley, Peter J

2013-11-01

Ammonia (NH3)-oxidizing bacteria (AOB) and thaumarchaea (AOA) co-occupy most soils, yet no short-term growth-independent method exists to determine their relative contributions to nitrification in situ. Microbial monooxygenases differ in their vulnerability to inactivation by aliphatic n-alkynes, and we found that NH3 oxidation by the marine thaumarchaeon Nitrosopumilus maritimus was unaffected during a 24-h exposure to ≤ 20 μM concentrations of 1-alkynes C8 and C9. In contrast, NH3 oxidation by two AOB (Nitrosomonas europaea and Nitrosospira multiformis) was quickly and irreversibly inactivated by 1 μM C8 (octyne). Evidence that nitrification carried out by soilborne AOA was also insensitive to octyne was obtained. In incubations (21 or 28 days) of two different whole soils, both acetylene and octyne effectively prevented NH4(+)-stimulated increases in AOB population densities, but octyne did not prevent increases in AOA population densities that were prevented by acetylene. Furthermore, octyne-resistant, NH4(+)-stimulated net nitrification rates of 2 and 7 μg N/g soil/day persisted throughout the incubation of the two soils. Other evidence that octyne-resistant nitrification was due to AOA included (i) a positive correlation of octyne-resistant nitrification in soil slurries of cropped and noncropped soils with allylthiourea-resistant activity (100 μM) and (ii) the finding that the fraction of octyne-resistant nitrification in soil slurries correlated with the fraction of nitrification that recovered from irreversible acetylene inactivation in the presence of bacterial protein synthesis inhibitors and with the octyne-resistant fraction of NH4(+)-saturated net nitrification measured in whole soils. Octyne can be useful in short-term assays to discriminate AOA and AOB contributions to soil nitrification.

Teratology study of amide derivatives of branched aliphatic carboxylic acids with 4-aminobenzensulfonamide in NMRI mice.

Science.gov (United States)

Onishi, Yuko; Okada, Akinobu; Noyori, Hiroko; Okamura, Ai; Hen, Naama; Yagen, Boris; Bialer, Meir; Fujiwara, Michio

2013-08-01

Valproic acid (VPA), widely used to treat epilepsy, bipolar disorders, and migraine prophylaxis, is known to cause neural tube and skeletal defects in humans and animals. Aminobenzensulfonamide derivatives of VPA with branched aliphatic carboxylic acids, namely 2-methyl-N-(4-sulfamoyl-phenyl)-pentanamide (MSP), 2-ethyl-N-(4-sulfamoyl-phenyl)-butyramide (ESB), 2-ethyl-4-methyl-N-(4-sulfamoyl-phenyl)-pentanamide (EMSP), and 2-ethyl-N-(4-sulfamoyl-benzyl)-butyramide (ESBB), have shown more potent anticonvulsant activity than VPA in preclinical testing. Here, we investigated the teratogenic effects of these analogous compounds of VPA in NMRI mice. Pregnant NMRI mice were given a single subcutaneous injection of either VPA at 1.8 or 3.6 mmol/kg, or MSP, ESB, EMSP, or ESBB at 1.8, 3.6, or 4.8 mmol/kg on gestation day (GD) 8. Cesarean section was performed on GD 18, and the live fetuses were examined for external and skeletal malformations. Compared with VPA, which induced neural tube defects (NTDs) in fetuses at 1.8 and 3.6 mmol/kg, the analog derivatives induced no NTDs at dose levels up to 4.8 mmol/kg (except for a single case of exencephaly at 4.8 mmol/kg MSP). Skeletal examination showed several abnormalities mainly at the axial skeletal level with VPA at 1.8 mmol/kg. Fused vertebrae and/or fused ribs were also observed with MSP, ESB, EMSP, and ESBB, they were less severe and seen at a lower incidence that those induced by VPA at the same dose level. In addition to exerting more potent preclinical antiepileptic activity, teratology comparison indicates that aminobenzensulfonamide analogs are generally more weakly teratogenic than VPA. © 2013 Wiley Periodicals, Inc.

Zn(II) coordination polymer of an in situ generated 4-pyridyl (4Py) attached bis(amido)phosphate ligand, [PO2(NH4Py)2]- showing preferential water uptake over aliphatic alcohols.

Science.gov (United States)

Gupta, Arvind K; Nagarkar, Sanjog S; Boomishankar, Ramamoorthy

2013-08-14

Two polymorphic 2D-coordination polymers of composition [ZnL(HCO2)]∞ were synthesized from an in situ generated ligand [PO2(NH(4)Py)2](-) (L(-)). The ligand L(-) was generated by a facile metal-assisted P-N bond hydrolysis reaction from the corresponding phosphonium salt 1, [P(NH(4)Py)4]Cl, or from the neutral phosphoric triamide 2, [PO(NH(4)Py)3]. The de-solvated sample of the polymer [ZnL(HCO2)]∞ features polar micropores and shows a type I isotherm for CO2 sorption whereas a type II behaviour was observed for N2. The vapour sorption isotherm of the de-solvated sample of [ZnL(HCO2)]∞ shows preferential adsorption of water vapour over aliphatic alcohols.

Investigation of test methods, material properties, and processes for solar cell encapsulants. Fourteenth quarterly progress report, August 12, 1978-November 12, 1979. [EVA, EPDM, aliphatic urethane, PVC plastisol, and butyl acrylate

Energy Technology Data Exchange (ETDEWEB)

Willis, P. B.; Baum, B.; Schnitzer, H. S.

1979-12-01

Springborn Laboratories is engaged in a study of evaluating potentially useful encapsulating materials for Task 3 of the Low-Cost Silicon Solar Array project (LSA) funded by DOE. The goal of this program is to identify, evaluate, and recommend encapsulant materials and processes for the production of cost-effective, long-life solar cell modules. This report presents the results of a cost analysis of candidate potting compounds for long life solar module encapsulation. Additionally, the two major encapsulation processes, sheet lamination and liquid casting, are costed on the basis of a large scale production facility. Potting compounds studied include EVA, sheet, clear; EVA, sheet, pigmented; EPDM, sheet, clear; Aliphatic urethane, syrup; PVC Plastisol; Butyl acrylate, syrup; and Butyl acrylate, sheet.

The effect of virtual cross linking on the oxidative stability and lipid uptake of aliphatic poly(urethane urea).

Science.gov (United States)

Thomas, Vinoy; Jayabalan, Muthu

2002-01-01

In vitro oxidative degradation and lipid sorption of aliphatic, low elastic modulus and virtually cross-linked poly(urethane urea)s based on 4,4' methylene bis(cyclohexyl isocyanate), hydroxy terminated poly butadiene and hexamethylene diamine were evaluated. The aged samples revealed no weight loss in the oxidation medium. The IR spectral analyses revealed the stability of unsaturated double bonds at 964 cm(-1) (characteristic for polybutadiene soft segment) with no change in peak intensity. The poly(tetramethylene glycol) (PTMG)-added poly(ether urethane urea) polymer also revealed no disappearance of IR peaks for ether and unsaturated double bonds in samples aged in vitro oxidation medium. All the polymers have shown increase in weight due to lipid up take in lipid-rich medium (palm oil) but it was rather low in Dulbecco's modified eagle medium (DMEM) cholesterol. The slight change in mechanical properties of the present polymers in oxidation and DMEM is due to the rearrangement of molecular structure with virtual cross links of hydrogen bonding (physical cross linking) without degradation and plasticization effect of lipid. The influence of these media on the rearrangement of virtual cross links has been observed. Higher the virtual cross-link density, lesser is the loss of tensile properties of poly(urethane urea)s in the oxidation medium and vice versa. On the other hand, higher the virtual cross-link density of poly(urethane urea), higher is the loss of ultimate tensile strength and stress at 100% strain and vice versa in DMEM medium.

Complexation of rhodium(II) tetracarboxylates with aliphatic diamines in solution: 1H and 13C NMR and DFT investigations.

Science.gov (United States)

Jaźwiński, Jarosław; Sadlej, Agnieszka

2013-10-01

The complexation of rhodium(II) tetraacetate, tetrakistrifluoroaceate and tetrakisoctanoate with a set of diamines (ethane-1,diamine, propane-1,3-diamine and nonane-1,9-diamine) and their N,N'-dimethyl and N,N,N',N'-tetramethyl derivatives in chloroform solution has been investigated by (1) H and (13) C NMR spectroscopy and density functional theory (DFT) modelling. A combination of two bifunctional reagents, diamines and rhodium(II) tetracarboxylates, yielded insoluble coordination polymers as main products of complexation and various adducts in the solution, being in equilibrium with insoluble material. All diamines initially formed the 2 : 1 (blue), (1 : 1)n oligomeric (red) and 1 : 2 (red) axial adducts in solution, depending on the reagents' molar ratio. Adducts of primary and secondary diamines decomposed in the presence of ligand excess, the former via unstable equatorial complexes. The complexation of secondary diamines slowed down the inversion at nitrogen atoms in NH(CH3 ) functional groups and resulted in the formation of nitrogenous stereogenic centres, detectable by NMR. Axial adducts of tertiary diamines appeared to be relatively stable. The presence of long aliphatic chains in molecules (adducts of nonane-1,9-diamines or rhodium(II) tetrakisoctanoate) increased adduct solubility. Hypothetical structures of the equatorial adduct of rhodium(II) tetraacetate with ethane-1,2-diamine and their NMR parameters were explored by means of DFT calculations. Copyright © 2013 John Wiley & Sons, Ltd.

N-terminal aliphatic residues dictate the structure, stability, assembly, and small molecule binding of the coiled-coil region of cartilage oligomeric matrix protein.

Science.gov (United States)

Gunasekar, Susheel K; Asnani, Mukta; Limbad, Chandani; Haghpanah, Jennifer S; Hom, Wendy; Barra, Hanna; Nanda, Soumya; Lu, Min; Montclare, Jin Kim

2009-09-15

The coiled-coil domain of cartilage oligomeric matrix protein (COMPcc) assembles into a homopentamer that naturally recognizes the small molecule 1,25-dihydroxyvitamin D(3) (vit D). To identify the residues critical for the structure, stability, oligomerization, and binding to vit D as well as two other small molecules, all-trans-retinol (ATR) and curcumin (CCM), here we perform an alanine scanning mutagenesis study. Ten residues lining the hydrophobic pocket of COMPcc were mutated into alanine; of the mutated residues, the N-terminal aliphatic residues L37, L44, V47, and L51 are responsible for maintaining the structure and function. Furthermore, two polar residues, T40 and Q54, within the N-terminal region when converted into alanine improve the alpha-helical structure, stability, and self-assembly behavior. Helical stability, oligomerization, and binding appear to be linked in a manner in which mutations that abolish helical structure and assembly bind poorly to vit D, ATR, and CCM. These results provide not only insight into COMPcc and its functional role but also useful guidelines for the design of stable, pentameric coiled-coils capable of selectively storing and delivering various small molecules.

Morphology and thermal properties of PLA films plasticized with aliphatic oligoesters; Morfologia e propriedades termicas de filmes de PLA plastificados com oligoesteres alifaticos

Energy Technology Data Exchange (ETDEWEB)

Inacio, Erika M.; Dias, Marcos L., E-mail: erika.minacio@ima.ufrj.br [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil); Lima, Maria Celiana P. [Instituto Federal do Rio de Janeiro (IFRJ), Duque de Caxias, RJ (Brazil)

2015-07-01

The addition of plasticizers to poly(lactic acid) (PLA) is one of the known ways of changing its ductility, making possible the modification of its mechanical and thermal properties. In this work, it was synthesized two biodegradable aliphatic oligoesters: oligo(trimethylene sebacate) (OST) and oligo(trimethylene malonate) (OMT), and these oligomers were used as plasticizer in cast films of commercial film grade PLA at concentrations of 1, 5 and 10 wt% of each plasticizer. X-ray diffraction (XRD) was used to investigate the morphology and differential scanning calorimetry (DSC) was also used aiming the evaluation of the thermal properties of these films. The PLA films containing no plasticizer showed an amorphous behavior, and the addition of PMT on the PLA films acted, simultaneously, decreasing the Tg, and rising the material's crystallinity. In contrast, the increased addition of OST to the PLA films did not change the Tg, and equally, did not have a significant changes in the material's crystallinity. Therefore, it was possible to observe the effect of the concentration of oligomers on the crystallinity of the films as well as the no plasticizer effect of the OST. (author)

Morphology and thermal properties of PLA films plasticised with aliphatic oligoesters; Morfologia e propriedades termicas de filmes de PLA plastificados com oligoesteres alifaticos

Energy Technology Data Exchange (ETDEWEB)

Inacio, Erika M.; Dias, Marcos L., E-mail: erika.minacio@ima.ufrj.br [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil); Lima, Maria Celiana P. [Instituto Federal do Rio de Janeiro (IFRJ), Duque de Caxias, RJ (Brazil)

2013-07-01

The addition of plasticizers to poly(lactic acid) (PLA) is one of the known ways of changing its ductility, making possible the modification of its mechanical and thermal properties. In this work, it was synthesized two biodegradable aliphatic oligoesters: oligo(trimethylene sebacate) (OST) and oligo(trimethylene malonate) (OMT), and these oligomers were used as plasticizer in cast films of commercial film grade PLA at concentrations of 1, 5 and 10 wt% of each plasticizer. X-ray diffraction (XRD) was used to investigate the morphology and differential scanning calorimetry (DSC) was also used aiming the evaluation of the thermal properties of these films. The PLA films containing no plasticizer showed an amorphous behavior, and the addition of PMT on the PLA films acted, simultaneously, decreasing the Tg, and rising the material's crystallinity. In contrast, the increased addition of OST to the PLA films did not change the Tg, and equally, did not have a significant changes in the material's crystallinity. Therefore, it was possible to observe the effect of the concentration of oligomers on the crystallinity of the films as well as the no plasticizer effect of the OST. (author)

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

Science.gov (United States)

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

Essential Oils Loaded in Nanosystems: A Developing Strategy for a Successful Therapeutic Approach

OpenAIRE

Bilia, Anna Rita; Guccione, Clizia; Isacchi, Benedetta; Righeschi, Chiara; Firenzuoli, Fabio; Bergonzi, Maria Camilla

2014-01-01

Essential oils are complex blends of a variety of volatile molecules such as terpenoids, phenol-derived aromatic components, and aliphatic components having a strong interest in pharmaceutical, sanitary, cosmetic, agricultural, and food industries. Since the middle ages, essential oils have been widely used for bactericidal, virucidal, fungicidal, antiparasitical, insecticidal, and other medicinal properties such as analgesic, sedative, anti-inflammatory, spasmolytic, and locally anaesthetic ...

Purification of di-nonyl phenyl phosphoric acid (DNPPA) for synergistic extraction of uranium from strong phosphoric acid

International Nuclear Information System (INIS)

Singh, D.K.; Vijayalakshmi, R.; Singh, H.; Sharma, J.N.; Ruhela, R.

2009-01-01

Di-nonyl phenyl phosphoric acid (DNPPA) obtained from various synthesis methods is always associated with impurities such as mono-nonyl phenyl phosphoric acid and nonyl phenol which need to be separated for its effective use in the extraction of uranium from strong phosphoric acid. Two methods of purification namely liquid-solid separation method using neodymium salt and liquid-liquid separation method using methylene glycol have been described. In the liquid solid separation method the purity of DNPPA obtained was about 95% with less than 1.0% monoester, however it heavily suffers in the recovery aspect which is of the order of 50-60%. The methylene glycol treatment method, results in high purity and recovery of the product. Purity obtained was about 95.0% diester and less than 0.5% monoester and recovery was more than 90%. Analysis of DNPPA was done by potentiometric titration method using autotitrator. (author)

Gc/ms analysis of coal tar composition produced from coal

African Journals Online (AJOL)

Coal pyrolysis is one of the significant approaches for the comprehensive utilization ... planigraphy-GC/MS; therefore a satisfactory analytical result obtained, which .... Among the aliphatic group of the coal tar, the proportion of alkene is larger ...

Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state (13)C NMR and solution (31)P NMR spectroscopy.

Science.gov (United States)

Liu, Shasha; Zhu, Yuanrong; Meng, Wei; He, Zhongqi; Feng, Weiying; Zhang, Chen; Giesy, John P

2016-02-01

Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state (13)C NMR and solution (31)P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O-C-O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH3 and COO/N-C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH3 and COO/N-C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis of new polyphosphonic acids, uranium extracting agents in a phosphoric medium

International Nuclear Information System (INIS)

Pensec, T.

1981-04-01

Synthesis of organic phosphorus compounds for liquid-liquid extraction of traces of uranium in concentrated phosphoric acid is studied in view of industrial applications. Diphosphonic acids and monoesters and also triphosphonic acids and related compounds are synthetized. Extraction tests show a better efficiency than OPPA [fr

Adsorption of Monobutyl Phthalate from Aqueous Phase onto Two Macroporous Anion-Exchange Resins

Directory of Open Access Journals (Sweden)

Zhengwen Xu

2014-01-01

Full Text Available As new emerging pollutants, phthalic acid monoesters (PAMs pose potential ecological and human health risks. In the present study, adsorption performance of monobutyl phthalate (MBP onto two macroporous base anion-exchange resins (D-201 and D-301 was discussed. It was found that the adsorption isotherms were best fitted by the Langmuir equation while the adsorption kinetics were well described by pseudo-first-order model. Analyses of sorption isotherms and thermodynamics proved that the adsorption mechanisms for DBP onto D-201 were ion exchange. However, the obtained enthalpy values indicate that the sorption process of MBP onto D-301 is physical adsorption. The equilibrium adsorption capacities and adsorption rates of DBP on two different resins increased with the increasing temperature of the solution. D-301 exhibited a higher adsorption capacity of MBP than D-201. These results proved that D-301, as an effective sorbent, can be used to remove phthalic acid monoesters from aqueous solution.

Characterization of carotenoid profiles in goldenberry (Physalis peruviana L.) fruits at various ripening stages and in different plant tissues by HPLC-DAD-APCI-MSn.

Science.gov (United States)

Etzbach, Lara; Pfeiffer, Anne; Weber, Fabian; Schieber, Andreas

2018-04-15

Carotenoid profiles of goldenberry (Physalis peruviana L.) fruits differing in ripening states and in different fruit fractions (peel, pulp, and calyx of ripe fruits) were investigated by HPLC-DAD-APCI-MS n . Out of the 53 carotenoids detected, 42 were tentatively identified. The carotenoid profile of unripe fruits is dominated by (all-E)-lutein (51%), whereas in ripe fruits, (all-E)-β-carotene (55%) and several carotenoid fatty acid esters, especially lutein esters esterified with myristic and palmitic acid as monoesters or diesters, were found. In overripe fruits, carotenoid conversion products and a higher proportion of carotenoid monoesters to diesters compared to ripe fruits were observed. Overripe fruits showed a significant decrease in total carotenoids of about 31% due to degradation. The observed conversion and degradation processes included epoxidation, isomerization, and deesterification. The peel of ripe goldenberries showed a 2.8 times higher total carotenoid content of 332.00 µg/g dw compared to the pulp. Copyright © 2017 Elsevier Ltd. All rights reserved.

Speed of sound in saturated aliphatic alcohols (propan-2-ol, butan-2-ol, and 2-methylpropan-1-ol) and alkanediols (ethane-1,2-diol, propane-1,2- and -1,3-diol) at temperature between 253.15 K and 353.15 K and pressures up to 30 MPa

International Nuclear Information System (INIS)

Dávila, María J.; Gedanitz, Holger; Span, Roland

2016-01-01

Highlights: • Speed of sound measurements were made in aliphatic alcohols and alkanediols. • Speeds of sound were measured in a wide temperature and pressure range. • A pulse-echo method with a double path type sensor operating at 8 MHz was employed. • A double polynomial equation was used to fit the experimental speed of sound data. • The accurate results were compared with available literature sources. - Abstract: Speeds of sound have been measured in three saturated aliphatic alcohols (propan-2-ol, butan-2-ol, and 2-methylpropan-1-ol) and three alkanediols (ethane-1,2-diol, propane-1,2- and -1,3-diol) in the temperature range from (253.15 to 353.15) K and pressures up to 30 MPa by use of a pulse-echo method with a double path type sensor operating at 8 MHz. The expanded overall uncertainties (k = 2) in the speed of sound measurements are estimated to be 0.013% for propan-2-ol, 0.019% for butan-2-ol, 0.01% for 2-methylpropan-1-ol, 0.009% for ethane-1,2-diol, 0.02% for propane-1,2-diol, and 0.07% for propane-1,3-diol. Experimental speeds of sound data were correlated with the temperature and pressure with an empirical double polynomial equation. Our results were also compared with the available literature data and a satisfactory agreement was found.

High regioselective acetylation of vitamin A precursors using lipase ...

African Journals Online (AJOL)

Administrator

2011-09-26

Sep 26, 2011 ... acetates, vinyl acetate gave the best yield. A maximum monoester ... All other chemicals were supplied by Sigma Chemical Co. The solvents were all of analytical grade. Enzymatic reactions. Reactions were conducted in screw-cap vials. ... suitable acyl donor to make reaction process irreversible. Various ...

Di-n-butyl Phthalate (DNBP) and Diisobutyl Phthalate (DiBP) Metabolism in a Human Volunteer after Single Oral Doses [Journal Article

Science.gov (United States)

An individual (male, 36 years, 87 kg) ingested two separate doses of di-n-butyl phthalate (DnBP) and diisobutyl phthalate (DiBP) at a rate of ~60 µg/kg. Key monoester and oxidized metabolites were identified and quantified in urine continuously collected until 48 hours post dos...

A study on the reactions of plant copper amine oxidase with C3 and C4 aliphatic diamines.

Science.gov (United States)

Sebela, M; Frébort, I; Lemr, K; Brauner, F; Pec, P

2000-12-01

The paper reports a study on the reactions of grass pea (Lathyrus sativus) amine oxidase (GPAO) with several aliphatic diamines. The influence of the chain length and of unsaturations in the molecules was examined. Kinetic measurements confirmed that trans-, i.e., (E)-2-butene-1,4-diamine (TDABE) and cis-, i.e., (Z)-2-butene-1,4-diamine (CDABE) could be classified as good substrates. Propane-1,3-diamine (DAP) and propene-1,3-diamine (DAPE) were only weakly oxidized, whereas 1,3-diamino-2-propanol (DAPL) was not utilized as a substrate. Contrary to the inactivator 2-butyne-1,4-diamine (DABI), DAPE was shown to be only a competitive inhibitor. DAP itself did not inhibit the catalytic activity. Irreversible inhibition of the activity occurred only after the incubation of GPAO with DABI; other diamines were without this effect. Differential pulse polarography and chromatofocusing confirmed that the aminoaldehyde product of DABI oxidation binds to the enzyme. Activity assay of pea aminoaldehyde dehydrogenase enabled us to detect the products of the oxidation of TDABE, CDABE, and DAP by GPAO. As the product of DAP oxidation, 3-amino-propanal (APAL) was detected by mass spectrometry and confirmed to be a potent noncompetitive inhibitor of GPAO. The absorption changes that occurred in the course of the reaction of GPAO with the diamines were investigated using rapid-scanning spectrophotometry. DABI, TDABE, CDABE, DAP, and DAPE reacted with GPAO providing characteristic maxima of the Cu(I)-semiquinolamine species that is formed in the catalytic cycle. The results presented here confirm that with the exception of DAPL, all the studied diamines could be classified as GPAO substrates, but only DABI can be considered as a mechanism-based inhibitor.

An avian equivalent of make-up?

NARCIS (Netherlands)

Piersma, T; Dekker, M; Damste, JSS; Sinninghe Damsté, Jaap S.; Lambrechts, M.

We report that a long-distance migrating shorebird, the red knot, makes a complete switch from commonly occurring monoester preen waxes to a much rarer class of higher-molecular-weight diester waxes at the time of take-off to the high arctic breeding grounds. The cold arctic climate would have

A new method for the determination of short-chain fatty acids from the aliphatic series in wines by headspace solid-phase microextraction-gas chromatography-ion trap mass spectrometry.

Science.gov (United States)

Olivero, Sergio J Pérez; Trujillo, Juan P Pérez

2011-06-24

A new analytical method for the determination of nine short-chain fatty acids (acetic, propionic, isobutyric, butyric, isovaleric, 2-methylbutyric, hexanoic, octanoic and decanoic acids) in wines using the automated HS/SPME-GC-ITMS technique was developed and optimised. Five different SPME fibers were tested and the influence of different factors such as temperature and time of extraction, temperature and time of desorption, pH, strength ionic, tannins, anthocyans, SO(2), sugar and ethanol content were studied and optimised using model solutions. Some analytes showed matrix effect so a study of recoveries was performed. The proposed HS/SPME-GC-ITMS method, that covers the concentration range of the different analytes in wines, showed wide linear ranges, values of repeatability and reproducibility lower than 4.0% of RSD and detection limits between 3 and 257 μgL(-1), lower than the olfactory thresholds. The optimised method is a suitable technique for the quantitative analysis of short-chain fatty acids from the aliphatic series in real samples of white, rose and red wines. Copyright © 2011 Elsevier B.V. All rights reserved.

Biosynthesis of acid phosphatase of baker's yeast . Characterization of a protoplast-bound fraction containing precursors of the exo-enzyme

NARCIS (Netherlands)

Boer, Pieter; Rijn, Herman J.M. van; Reinking, A.; Steyn-Parvé, Elizabeth P.

1975-01-01

1. 1.|Yest protoplasts, secreting acid phosphatase (orthophosphoric-monoester phosphohydrolase (acid optimum) EC 3.1.3.2) contain a small amount of firmly bound enzyme, even after lysis (Van Rijn, H.J.M.; Boer, P. and Steyn-Parvé, E.P. (1972) Biochim. Biophys. Acta 268, 431–441). The major part

Patterns and sources of particle-phase aliphatic and polycyclic aromatic hydrocarbons in urban and rural sites of western Greece

Science.gov (United States)

Kalaitzoglou, Maria; Terzi, Eleni; Samara, Constantini

Particle-bound aliphatic and polycyclic aromatic hydrocarbons (AHs and PAHs, respectively) were determined in the ambient air of the Eordea basin, in western Greece, where intensive coal burning for power generation takes place. Thirteen PAHs, n-alkanes (C 14-C 35), hopanes, and isoprenoid hydrocarbons (pristane and phytane) were determined in the total suspended particles collected from the atmosphere of four sites within the basin receiving potential impacts from various sources, such as fly ash, coal mining, automobile traffic, domestic heating, and agricultural or refuse burning. The same organic species were also determined in the fly ash generated in power stations, and in particulate emissions from open burning of biomass (dry corn leaves) and refuse burning. Organic particle sources were resolved using concentration diagnostic ratios and factor analysis (FA). A multivariate statistical receptor model (Absolute Principal Component Analysis, APCA) was finally employed to estimate the contribution of identified sources to the measured concentrations of organic pollutants. Four major sources for ambient PAHs and AHs were identified displaying variable contribution in different sites: (a) fossil fuel combustion, (b) biogenic emissions, (c) refuse burning, and (d) oil residues. Fuel combustion was the major source of ambient PAHs and an important source of n-alkanes in the range C 21-C 28. Oil residues were found to be the major source of low molecular weight n-alkanes (particularly the C 14-C 16), and an important source of pristane, phytane and UCM. Biogenic sources were primarily responsible for the high molecular weight n-alkanes explaining almost the entire concentration levels of homologues >C 32. Biomass burning was particularly important for the C 23-C 26n-alkanes. Despite the vicinity of certain sampling sites to power stations, coal fly ash was not identifiable as a source for ambient PAHs and AHs.

Characterization of the rate and temperature sensitivities of bacterial remineralization of dissolved organic phosphorus by natural populations

Directory of Open Access Journals (Sweden)

Angelicque E. White

2012-08-01

Full Text Available Production, transformation, and degradation are the principal components of the cycling of dissolved organic matter (DOM in marine systems. Heterotrophic Bacteria (and Archaea play a large part in this cycling via enzymatic decomposition and intracellular transformations of organic material to inorganic carbon (C, nitrogen (N , and phosphorus (P. The rate and magnitude of inorganic nutrient regeneration from DOM is related to the elemental composition and lability of DOM substrates as well as the nutritional needs of the mediating organisms. While many previous efforts have focused on C and N cycling of DOM, less is known in regards to the controls of organic P utilization and remineralization by natural populations of bacteria. In order to constrain the relative time scales and degradation of select dissolved organic P (DOP compounds we have conducted a series of experiments focused on (1 assessment of the short-term lability of a range of DOP compounds, (2 characterization of labile DOP remineralization rates and (3 examination of temperature sensitivities of labile DOP remineralization for varying bacterial populations. Results reinforce previous findings of monoester and polyphosphate lability and the relative recalcitrance of a model phosphonate: 2-aminoethylphosphonate. High resolution time-series of P monoester remineralization indicates decay constants on the order of 0.67-7.04 d-1 for bacterial populations isolated from coastal and open ocean surface waters. The variability of these rates is predictably related to incubation temperature and initial concentrations of heterotrophic bacteria. Additional controls on DOP hydrolysis included seasonal shifts in bacterial populations and the physiological state of bacteria at the initiation of DOP addition experiments. Composite results indicate that bacterial hydrolysis of P-monoesters exceeds bacterial P demand and thus DOP remineralization efficiency may control P availability to autotrophs.

The development of orally administrable gemcitabine prodrugs with D-enantiomer amino acids: enhanced membrane permeability and enzymatic stability.

Science.gov (United States)

Tsume, Yasuhiro; Incecayir, Tuba; Song, Xueqin; Hilfinger, John M; Amidon, Gordon L

2014-04-01

Gemcitabine prodrugs with D- and L-configuration amino acids were synthesized and their chemical stability in buffers, resistance to glycosidic bond metabolism, enzymatic activation, permeability in Caco-2 cells and mouse intestinal membrane, anti-proliferation activity in cancer cell were determined and compared to that of parent drug, gemcitabine. Prodrugs containing D-configuration amino acids were enzymatically more stable than ones with L-configuration amino acids. The activation of all gemcitabine prodrugs was 1.3-17.6-fold faster in cancer cell homogenate than their hydrolysis in buffer, suggesting enzymatic action. The enzymatic activation of amino acid monoester prodrugs containing D-configuration amino acids in cell homogenates was 2.2-10.9-fold slower than one of amino acid monoester prodrugs with L-configuration amino acids. All prodrugs exhibited enhanced resistance to glycosidic bond metabolism by thymidine phosphorylase compared to parent gemcitabine. Gemcitabine prodrugs showed superior the effective permeability in mouse jejunum to gemcitabine. More importantly, the high plasma concentration of d-amino acid gemcitabine prodrugs was observed more than one of L-amino acid gemcitabine prodrugs. In general, the 5'-mono-amino acid monoester gemcitabine prodrugs exhibited higher permeability and uptake than their parent drug, gemcitabine. Cell proliferation assays in AsPC-1 pancreatic ductal cell line indicated that gemcitabine prodrugs were more potent than their parent drug, gemcitabine. The transport and enzymatic profiles of 5'-D-valyl-gemcitabine and 5'-D-phenylalanyl-gemcitabine suggest their potential for increased oral uptake and delayed enzymatic bioconversion as well as enhanced uptake and cytotoxic activity in cancer cells, would facilitate the development of oral dosage form for anti-cancer agents and, hence, improve the quality of life for the cancer patients. Copyright © 2014. Published by Elsevier B.V.

Partial molar volumes of organic solutes in water. XXVIII. Three aliphatic poly(ethylene glycols) at temperatures T = 298 K–573 K and pressures up to 30 MPa

International Nuclear Information System (INIS)

Cibulka, Ivan

2017-01-01

Highlights: • Standard molar volumes of three poly(ethylene glycols) in water are presented. • Data were obtained in the range T from (298 to 573) K and p up to 30 MPa. • Data are analyzed and compared with those of similar solutes. - Abstract: Densities of dilute aqueous solutions of three poly(ethylene glycols): 3-oxapentane-1,5-diol (diethylene glycol), 3,6-dioxaoctane-1,8-diol (triethylene glycol), and 3,5,9-trioxaundecane-1,11-diol (tetraethylene glycol) measured in the temperature range from (298 to 573) K and at pressures up to 30 MPa using an automated flow vibrating-tube densimeter are reported. Standard molar volumes were evaluated from the measured data. Present data complement both the previous measurements performed at atmospheric pressure in the temperature range from (278 to 343) K and the data already available for the first member of the homologous series (ethylene glycol). A comparison with data previously measured for the homologous series of linear aliphatic polyethers (poly(ethylene glycol) dimethyl ethers, glymes), diethylene glycol monomethyl ether (3,6-dioxaheptan-1-ol), and selected alkane-α,ω-diols is presented.

Novel approaches to the creation of alternative motor fuels from renewable raw materials

Directory of Open Access Journals (Sweden)

Ольга Олександрівна Гайдай

2016-06-01

Full Text Available The paper considers the method of obtaining aliphatic alcohols as components of alternative fuels by catalytic processing of synthesis gas under the conditions of mechanochemical activation of the catalyst without using high pressure.It is established that the introduction of hydrocarbon spherical clusters (onions in the alternative fuel changes physical, chemical and chemmotological characteristics of fuel due to the effect of structure formation. The results of comparative studies of the performance properties of hydrocarbon and alternative fuels are displayed

Grafting of 2 (2-hydroxy-5-vinylphenyl) 2H-benzotriazole onto polymers with aliphatic groups. Synthesis and polymerization of 2 (2-hydroxy-5-isopropenylphenyl) 2H-benzotriazole and a new synthesis of 2 (2-hydroxy-5-vinylphenyl) 2H-benzotriazole

Science.gov (United States)

Pradellok, W.; Nir, Z.; Vogl, O.

1981-01-01

Successful grafting of 2(2-hydroxy-5-vinylphenyl)2H-benzotriazole onto saturated aliphatic C-H groups of polymers has been accomplished. When the grafting reaction was carried out in chlorobenzene at 150 C = 160 C with di-tertiarybutylperoxide as the grafting initiator, grafts as high as 20 percent - 30 percent at a grafting efficiency of 50 percent and 80 percent have readily been obtained. The grafting reaction was carried out in tubes sealed under high vacuum since trace amounts of oxygen cause complete inhibition of the grafting reaction by the phenolic monomer. On a variety of different polymers including atactic polypropylene, ethylene/vinyl acetate copolymer, poly(methyl methacrylate), poly(butyl acrylate), and polycarbonate were used.

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.

Science.gov (United States)

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.

DETECTING LOW-LEVEL SYNTHESIS IMPURITIES IN MODIFIED PHOSPHOROTHIOATE OLIGONUCLEOTIDES USING LIQUID CHROMATOGRAPHY – HIGH RESOLUTION MASS SPECTROMETRY

Science.gov (United States)

Nikcevic, Irena; Wyrzykiewicz, Tadeusz K.; Limbach, Patrick A.

2010-01-01

Summary An LC-MS method based on the use of high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS) for profiling oligonucleotides synthesis impurities is described. Oligonucleotide phosphorothioatediesters (phosphorothioate oligonucleotides), in which one of the non-bridging oxygen atoms at each phosphorus center is replaced by a sulfur atom, are now one of the most popular oligonucleotide modifications due to their ease of chemical synthesis and advantageous pharmacokinetic properties. Despite significant progress in the solid-phase oligomerization chemistry used in the manufacturing of these oligonucleotides, multiple classes of low-level impurities always accompany synthetic oligonucleotides. Liquid chromatography-mass spectrometry has emerged as a powerful technique for the identification of these synthesis impurities. However, impurity profiling, where the entire complement of low-level synthetic impurities is identified in a single analysis, is more challenging. Here we present an LC-MS method based the use of high resolution-mass spectrometry, specifically Fourier transform ion cyclotron resonance mass spectrometry (FTIRCMS or FTMS). The optimal LC-FTMS conditions, including the stationary phase and mobile phases for the separation and identification of phosphorothioate oligonucleotides, were found. The characteristics of FTMS enable charge state determination from single m/z values of low-level impurities. Charge state information then enables more accurate modeling of the detected isotopic distribution for identification of the chemical composition of the detected impurity. Using this approach, a number of phosphorothioate impurities can be detected by LC-FTMS including failure sequences carrying 3′-terminal phosphate monoester and 3′-terminal phosphorothioate monoester, incomplete backbone sulfurization and desulfurization products, high molecular weight impurities, and chloral, isobutyryl, and N3 (2-cyanoethyl) adducts

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

Science.gov (United States)

Matasović, Brunislav; Bonifačić, Marija

2011-06-01

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals CO2-rad , rad CH 2OH, rad CH(CH 3)OH, and rad CH(CH 3)O - have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production 60Co γ-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U rad radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U rad radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of α-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism ( Matasović and Bonifačić, 2007). Thus, while both rad CH 2OH and rad CH(CH 3)OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm -3 concentrations, pH 7, brought about chain debromination to occur in the case of rad CH(CH 3)OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of α-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U rad radicals have been estimated to amount to about ≥85 and 1200 dm 3 mol -1 s -1, respectively.

S Sivaram, NCL, Pune

Indian Academy of Sciences (India)

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Sustainable materials based on aliphatic polyesters: Teaching old chemistry some new tricks. Aliphatic polyesters, a ... strategies to get around these limitations. Many such strategies have emerged in ... This lecture will highlight current challenges in the synthesis of aliphatic polyesters using a wide variety of monomers and ...

NSP-Dependent Simple Nitrile Formation Dominates upon Breakdown of Major Aliphatic Glucosinolates in Roots, Seeds, and Seedlings of Arabidopsis thaliana Columbia-0.

Science.gov (United States)

Wittstock, Ute; Meier, Kathrin; Dörr, Friederike; Ravindran, Beena M

2016-01-01

One of the best-studied plant defense systems, the glucosinolate-myrosinase system of the Brassicales, is composed of thioglucosides known as glucosinolates and their hydrolytic enzymes, the myrosinases. Tissue disruption brings these components together, and bioactive products are formed as a consequence of myrosinase-catalyzed glucosinolate hydrolysis. Among these products, isothiocyanates have attracted most interest as chemical plant defenses against herbivores and pathogens and health-promoting compounds in the human diet. Previous research has identified specifier proteins whose presence results in the formation of alternative product types, e.g., nitriles, at the expense of isothiocyanates. The biological roles of specifier proteins and alternative breakdown products are poorly understood. Here, we assessed glucosinolate breakdown product profiles obtained upon maceration of roots, seedlings and seeds of Arabidopsis thaliana Columbia-0. We identified simple nitriles as the predominant breakdown products of the major endogenous aliphatic glucosinolates in root, seed, and seedling homogenates. In agreement with this finding, genes encoding nitrile-specifier proteins (NSPs) are expressed in roots, seeds, and seedlings. Analysis of glucosinolate breakdown in mutants with T-DNA insertions in any of the five NSP genes demonstrated, that simple nitrile formation upon tissue disruption depended almost entirely on NSP2 in seeds and mainly on NSP1 in seedlings. In roots, about 70-80% of the nitrile-forming activity was due to NSP1 and NSP3 . Thus, glucosinolate breakdown product profiles are organ-specifically regulated in A. thaliana Col-0, and high proportions of simple nitriles are formed in some parts of the plant. This should be considered in future studies on biological roles of the glucosinolate-myrosinase system.

Distribution and evolution of sterols and aliphatic hydrocarbons in dated marine sediment cores from the Cabo Frio upwelling region, SW Atlantic, Brazil.

Science.gov (United States)

Lourenço, Rafael André; Martins, César C; Taniguchi, Satie; Mahiques, Michel Michaelovitch; Montone, Rosalinda Carmela; Magalhães, Caio Augusto; Bícego, Márcia Caruso

2017-08-01

We report the distribution of selected lipid biomarkers specifically sterols and aliphatic hydrocarbons in sediment cores from Cabo Frio, SW Atlantic continental shelf, Brazil, corresponding approximately to the last 700 years. In the Cabo Frio region, a costal upwelling occurs as a quasi-seasonal phenomenon characterized by nutrient-rich bottom waters that intrude on the continental shelf and promote relatively high biological productivity compared to other Brazilian continental shelf areas. The results for sterols indicate the predominance of organic matter (OM) inputs related to marine organisms, mainly plankton, in all of the cores along the time scale studied. Principal component analyses show three different groups of variables, which may be associated with (i) the more effective intrusion of the nutrient-rich South Atlantic Central Water, resulting in the increase of marine lipid biomarkers such as sterols and short-chain n-alkanes; (ii) the influence of the Coastal Water with higher surface water temperature and subsequently lower primary productivity; and (iii) OM characterized by high total organic carbon and long-chain n-alkanes related to an allochthonous source. Relatively high concentrations of sterols and n-alkanes between 1450 and 1700 AD, chronologically associated with the Little Ice Age, suggest a period associated with changes in the local input of specific sources of these compounds. The concentrations of lipid biomarkers vary over core depth, but this does not suggest a notably high or low intensity of upwelling processes. It is possible that the climatic and sea surface temperature changes reported in previous studies did not affect the input of the sedimentary lipid biomarkers analyzed here.

NSP-dependent simple nitrile formation dominates upon breakdown of major aliphatic glucosinolates in roots, seeds, and seedlings of Arabidopsis thaliana Columbia-0

Directory of Open Access Journals (Sweden)

Ute Wittstock

2016-12-01

Full Text Available One of the best-studied plant defense systems, the glucosinolate-myrosinase system of the Brassicales, is composed of thioglucosides known as glucosinolates and their hydrolytic enzymes, the myrosinases. Tissue disruption brings these components together, and bioactive products are formed as a consequence of myrosinase-catalyzed glucosinolate hydrolysis. Among these products, isothiocyanates have attracted most interest as chemical plant defenses against herbivores and pathogens and health-promoting compounds in the human diet. Previous research has identified specifier proteins whose presence results in the formation of alternative product types, e.g. nitriles, at the expense of isothiocyanates. The biological roles of specifier proteins and alternative breakdown products are poorly understood. Here, we assessed glucosinolate breakdown product profiles obtained upon maceration of roots, seedlings and seeds of Arabidopsis thaliana Columbia-0. We identified simple nitriles as the predominant breakdown products of the major endogenous aliphatic glucosinolates in root, seed, and seedling homogenates. In agreement with this finding, genes encoding nitrile-specifier proteins (NSPs are expressed in roots, seeds, and seedlings. Analysis of glucosinolate breakdown in mutants with T-DNA insertions in any of the five NSP genes demonstrated, that simple nitrile formation upon tissue disruption depended almost entirely on NSP2 in seeds and mainly on NSP1 in seedlings. In roots, about 70-80 % of the nitrile-forming activity was due to NSP1 and NSP3. Thus, glucosinolate breakdown product profiles are organ-specifically regulated in A. thaliana Col 0, and high proportions of simple nitriles are formed in some parts of the plant. This should be considered in future studies on biological roles of the glucosinolate-myrosinase system.

High performance liquid chromatography analysis of aliphatic thiols in alimentary supplements and pharmaceuticals using menadione as a new useful derivatization reagent.

Science.gov (United States)

Gatti, Rita; Vitellaro, Valeria

2013-12-04

The use of menadione (MD) as a pre-column reagent for high performance liquid chromatography (HPLC) analysis of aliphatic thiols is proposed. The reaction was carried out for 5 min at room temperature and pH 8.5. The developed method was applied to the N-acetylcysteine (NAC) analysis of alimentary supplements and pharmaceutical formulations. The effect of the complex matrix was evaluated by the study of the thiol derivatization reaction both in standard and in placebo solutions. The yield of NAC-MD adduct was found to be quantitative at a reagent to thiol molar ratio of about 4 in comparison with an authentic specimen of synthesized NAC adduct, which was characterized by (1)H NMR, IR and UV. The routine chromatographic separations were performed on a Synergi MAX-RP column using a mobile phase consisting of methanol/triethylammonium (TEA) phosphate buffer (pH 3; 0.05 mol L(-1)) 70:30 (v/v) at a flow-rate of 0.4 mL min(-1). UV-diode array detection was used setting the wavelength at λ=260 nm. The validation parameters such as linearity, sensitivity, accuracy, precision, selectivity and ruggedness were found to be highly satisfactory. Similar linear responses were observed by standard and placebo solutions (determination coefficient: 0.9996). Limit of detection was about 0.019 μg g(-1). Intra-day precision (relative standard deviation, R.S.D.) was ≤0.81% for NAC to internal standard (IS) peak area ratio, ≤0.28% and ≤0.32%, respectively, for NAC and IS retention times (tR), without significant differences between intra- and inter-day data. NAC recovery studies gave good results (100.12%) with R.S.D.=1.05%. Copyright © 2013 Elsevier B.V. All rights reserved.

Urinary Phthalate Metabolites in American Alligators (Alligator mississippiensis) from Selected Florida Wetlands.

Science.gov (United States)

Brock, John W; Bell, Jane Margaret; Guillette, Louis J

2016-07-01

Phthalates have been shown to cause endocrine disruption in laboratory animals and are associated with altered development of the reproductive system in humans. Further, human have significant exposure to phthalates. However, little is known concerning the exposure of wildlife to phthalates. We report urinary phthalate metabolite concentrations from fifty juvenile alligators from three Florida lakes and a site in the Everglades. Urinary phthalate monoester concentrations varied widely among alligators from the different sites but also among alligators from the same site. Mono-2-ethylhexy phthalate and monobutyl phthalate were found in most samples of alligator urine with maximums of 35,700 ng/mL and 193 ng/mL, respectively. Monobenzyl phthalate was found in 5 alligators with a maximum of 66.7 ng/mL. Other monoesters were found in only one or two alligator urine samples. The wide variation within and among sites, in addition to the high levels of mEHP, mBP and mBzP, is consistent with exposure arising from the intermittent spraying of herbicide formulations to control invasive aquatic plants in Florida freshwater sites. Phthalate diesters are used as adjuvants in many of these formulations.

[Effects of steaming and baking on content of alkaloids in Aconite Lateralis Radix (Fuzi)].

Science.gov (United States)

Yang, Chang-lin; Huang, Zhi-fang; Zhang, Yi-han; Liu, Yu-hong; Liu, Yun-huan; Chen, Yan; Yi, Jin-hai

2014-12-01

To study the effect of steaming and baking process on contents of alkaloids in Aconite Lateralis Radix (Fuzi), 13 alkaloids were analyzed by UPLC-MS/MS equipped with ESI ion source in MRM mode. In steaming process, the contents of diester-diterpenoid alkaloids decreased rapidly, the contents of monoester-diterpenoid alkaloids firstly increased, reached the peak at 40 min, and then deceased gradually. The contents of aconine alkaloids (mesaconine, aconine and hypaconine) increased all the time during processing, while the contents of fuziline, songorine, karacoline, salsolionl were stable or slightly decreased. In baking process, dynamic variations of alkaloids were different from that in the steaming process. Diester-diterpenoid alkaloids were degraded slightly slower than in steaming process. Monoester-diterpenoid alkaloids, aconine alkaloids and the total alkaloids had been destroyed at different degrees, their contents were significantly lower than the ones in steaming Fuzi at the same processing time. This experiment revealed the dynamic variations of alkaloids in the course of steaming and baking. Two processing methods which can both effectively remove the toxic ingredients and retain the active ingredients are simple and controllable, and are valuable for popularization and application.

Species and biogeochemical cycles of organic phosphorus in sediments from a river with different aquatic plants located in Huaihe River Watershed, China.

Science.gov (United States)

Yuan, He Zhong; Pan, Wei; Ren, Li Jun; Liu, Eeng Feng; Shen, Ji; Geng, Qi Fang; An, Shu Qing

2015-01-01

The results of phosphorus fractionation in the sediments from a contaminated river containing different aquatic plants, analyzed by solution 31P-NMR for Organic Phosphorus, showed that the concentration of Inorganic Phosphorus dominated in all species and Organic Phosphorus accounted for over 20% of Total Phosphorus. In general, orthophosphate was dominant in all the sampling sites. The proportion of Organic Phosphorus accounting for the Total Phosphorus in the sediments with different plant decreased in the following order: Paspalum distichum>Typha orientalis>Hydrilla verticillata. Phosphorus-accumulation ability of Paspalum distichum was obviously stronger than Typha orientalis and Hydrilla verticillata. The Organic Phosphorus was in aquatic plants dominated by humic-associated P (Hu-P), which converted to Inorganic Ohosphorus more significantly in submerged plants than in emerged plants. The sediment dominated by Paspalum distichum abundantly accumulated Organic Phosphorus in the orthophosphate monoester fraction. The degradation and mineralization of orthophosphate monoester was the important source of high Inorganic Phosphorus concentration and net primary productivity in Suoxu River. The Organic Phosphorus derived from Typha orientalis and Hydrilla verticillata was dramatically converted to Inorganic Phosphorus when the environmental factors varied.

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

Science.gov (United States)

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.

Multiscale approach to the morphology, structure, and segmental dynamics of complex degradable aliphatic polyurethanes

Czech Academy of Sciences Publication Activity Database

Špírková, Milena; Machová, Luďka; Kobera, Libor; Brus, Jiří; Poreba, Rafal; Serkis, Magdalena; Zhigunov, Alexander

2015-01-01

Roč. 132, č. 10 (2015), 41590_1-41590_11 ISSN 0021-8995 R&D Projects: GA ČR(CZ) GA13-06700S Institutional support: RVO:61389013 Keywords : elastomers * nanostructured polymers * polyurethanes Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.866, year: 2015

Development of a near-infrared spectroscopy method (NIRS) for fast analysis of total, indolic, aliphatic and individual glucosinolates in new bred open pollinating genotypes of broccoli (Brassica oleracea convar. botrytis var. italica).

Science.gov (United States)

Sahamishirazi, Samira; Zikeli, Sabine; Fleck, Michael; Claupein, Wilhelm; Graeff-Hoenninger, Simone

2017-10-01

This study describes the development of near-infrared spectroscopy (NIRS) calibration to determine individual and total glucosinolates (GSLs) content of 12 new-bred open-pollinating genotypes of broccoli (Brassica oleracea convar. botrytis var. italica). Six individual GSLs were identified using high-performance-liquid chromatography (HPLC). The NIRS calibration was established based on modified partial least squares regression with reference values of HPLC. The calibration was analyzed using coefficient of determination in prediction (R 2 ) and ratio of preference of determination (RPD). Large variation occurred in the calibrations, R 2 and RPD due to the variability of the samples. Derived calibrations for total-GSLs, aliphatic-GSLs, glucoraphanin and 4-methoxyglucobrassicin were quantitative with a high accuracy (RPD=1.36, 1.65, 1.63, 1.11) while, for indole-GSLs, glucosinigrin, glucoiberin, glucobrassicin and 1-methoxyglucobrassicin were more qualitative (RPD=0.95, 0.62, 0.67, 0.81, 0.56). Overall, the results indicated NIRS has a good potential to determine different GSLs in a large sample pool of broccoli quantitatively and qualitatively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rhodium-catalyzed Asymmetric Hydrogenation of α-Dehydroamino Ketones: A General Approach to Chiral α-amino Ketones.

Science.gov (United States)

Gao, Wenchao; Wang, Qingli; Xie, Yun; Lv, Hui; Zhang, Xumu

2016-01-01

Rhodium/DuanPhos-catalyzed asymmetric hydrogenation of aliphatic α-dehydroamino ketones has been achieved and afforded chiral α-amino ketones in high yields and excellent enantioselectives (up to 99 % ee), which could be reduced further to chiral β-amino alcohols by LiAlH(tBuO)3 with good yields. This protocol provides a readily accessible route for the synthesis of chiral α-amino ketones and chiral β-amino alcohols. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Differences of diurnal variations of some aliphatic and polycyclic aromatic hydrocarbons concentrations in aerosols of the urban area of Madrid; Estudio de las variaciones diarias en las concentraciones de algunos hidrocarburos alifaticos y aromatico; policiclicos, en aerosoles de la zona urbana de Madrid

Energy Technology Data Exchange (ETDEWEB)

Perez, M M; Perez-Pastor, R M; Bea, F J; Campos, A; Gonzalez, D

1991-07-01

A study on daily concentration changes of polycyclic aromatic and aliphatic hydrocarbons (PAH's and AH's), was carried out in aerosols sampled m the Ciudad Universitaria of Madrid. Samples were taken at morning and night during February and June, for short sampling times, on glass fiber filters in Hi-Vol samplers, and then extracted ultrasonically with cyclohexane. Analysis were performed by HRGC with fused-silica capillary columns. The variable traffic rate, and the strong influence during winter periods of domestic heating are characteristic of this place. The aim of this work was to evaluate diurnal and seasonal variations of selected AH and PAH in the urban area of Madrid, by using descriptive parameters, such as total concentrations of AH and PAH, characteristic profiles and predominance carbon index. (Author)

Chemical modification of carbon powders with aminophenyl and aryl-aliphatic amine groups by reduction of in situ generated diazonium cations: Applicability of the grafted powder towards CO{sub 2} capture

Energy Technology Data Exchange (ETDEWEB)

Aurelie Grondein; Daniel Belanger [Universite du Quebec a Montreal, Montreal, PQ (Canada). Departement de Chimie

2011-08-15

Aminophenyl, p-aminobenzyl and p-aminoethylphenyl groups were grafted at the surface of carbon Vulcan XC72R by spontaneous reduction of the in situ generated diazonium cations from the corresponding amine. X-ray photoelectron spectroscopy and elemental analysis confirmed an amine loading of about 1 mmol/g. The grafting of amine functionalities leads to a decrease of specific surface area from 223 to about 110 m{sup 2}/g with a drastic loss of microporosity. Acid-base properties of the surface are also affected by the modification. Aminophenyl grafted groups make the surface more acidic while aryl-aliphatic amines groups tends to render it more basic. The grafted layer shows in each case a good thermal stability up to 250{sup o}C. The affinity of the modified powder towards CO{sub 2} and N{sub 2} has been evaluated by thermal swing adsorption. The maximum adsorption capacity of CO{sub 2} of modified carbons is lower than the unmodified carbon but the presence of the amine functionalities involves a better selectivity of the material towards CO{sub 2} adsorption in comparison of N{sub 2} adsorption. 53 refs., 9 figs., 3 tabs.

EFSA ; Scientific Opinion on Flavouring Group Evaluation 98 (FGE.98): Consideration of three ring-unsaturated delta-lactones)

DEFF Research Database (Denmark)

Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of three unsaturated delta-lactones [FL-no: 10.031, 10.037 and 10.044] previously evaluated by the JECFA at their 49th meeting in 1997. The JECFA considered that further information...... on the metabolism of these three substances was required and that they should be evaluated together with other substances containing alpha,beta-unsaturation and that, therefore, their evaluation should be deferred. However, the EFSA Panel has considered that these three JECFA evaluated aliphatic lactones can...... be hydrolysed and metabolised to innocuous products in line with the aliphatic lactones evaluated by EFSA in FGE.10Rev2. The substances were evaluated through a stepwise approach that integrates information on structure-activity relationships, intake from current uses, toxicological threshold of concern...

Selection of side-chain carbons in a high-molecular-weight, hydrophobic peptide using solid-state spectral editing methods

International Nuclear Information System (INIS)

Kumashiro, Kristin K.; Niemczura, Walter P.; Kim, Minna S.; Sandberg, Lawrence B.

2000-01-01

Solid-state spectral editing techniques have been used by others to simplify 13 C CPMAS spectra of small organic molecules, synthetic organic polymers, and coals. One approach utilizes experiments such as cross-polarization-with-polarization-inversion and cross-polarization-with-depolarization to generate subspectra. This work shows that this particular methodology is also applicable to natural-abundance 13 C CPMAS NMR studies of high-molecular-weight biopolymers. The editing experiments are demonstrated first with model peptides and then with α-elastin, a high-molecular-weight peptidyl preparation obtained from the elastic fibers in mammalian tissue. The latter has a predominance of small, nonpolar residues, which is evident in the crowded aliphatic region of typical 13 C CPMAS spectra. Spectral editing is particularly useful for simplifying the aliphatic region of the NMR spectrum of this elastin preparation

Supramolecular Recognition Allows Remote, Site-Selective C-H Oxidation of Methylenic Sites in Linear Amines.

Science.gov (United States)

Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel

2017-12-18

Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp 3 )-H hydroxylation with H 2 O 2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C-H bonds, no matter the chain length. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel approaches to analysis of 3-chloropropane-1,2-diol esters in vegetable oils.

Science.gov (United States)

Moravcova, Eliska; Vaclavik, Lukas; Lacina, Ondrej; Hrbek, Vojtech; Riddellova, Katerina; Hajslova, Jana

2012-03-01

A sensitive and accurate method utilizing ultrahigh performance liquid chromatography (U-HPLC) coupled to high resolution mass spectrometry based on orbitrap technology (orbitrapMS) for the analysis of nine 3-chloropropane-1,2-diol (3-MCPD) diesters in vegetable oils was developed. To remove the interfering triacylglycerols that induce strong matrix effects, a clean-up step on silica gel column was used. The quantitative analysis was performed with the use of deuterium-labeled internal standards. The lowest calibration levels estimated for the respective analytes ranged from 2 to 5 μg kg(-1). Good recovery values (89-120%) and repeatability (RSD 5-9%) was obtained at spiking levels of 2 and 10 mg kg(-1). As an alternative, a novel ambient desorption ionization technique, direct analysis in real time (DART), hyphenated with orbitrapMS, was employed for no separation, high-throughput, semi-quantitative screening of 3-MCPD diesters in samples obtained by chromatographic fractionation. Additionally, the levels of 3-MCPD diesters measured in reallife vegetable oil samples (palm oil, sunflower oil, rapeseed oil) using both methods are reported. Relatively good agreement of the data generated by U-HPLC-orbitrapMS and DART-orbitrapMS were observed. With regard to a low ionization yield achieved for 3-MCPD monoesters, the methods presented in this paper were not yet applicable for the analysis of these contaminants at the naturally occurring levels.

Disruption of Retinol (Vitamin A Signaling by Phthalate Esters: SAR and Mechanism Studies.

Directory of Open Access Journals (Sweden)

Yanling Chen

Full Text Available A spectrum of reproductive system anomalies (cryptorchidism, hypospadias, dysgenesis of Wolffian duct-derived tissues and prostate, and reduced sperm production in male rats exposed in utero to phthalate esters (PEs are thought to be caused by PE inhibition of fetal testosterone production. Recently, dibutyl and dipentyl phthalate (DBuP, DPnP were shown to disrupt the retinol signaling pathway (RSP in mouse pluripotent P19 embryonal carcinoma cells in vitro. The RSP regulates the synthesis and cellular levels of retinoic acid (RA, the active metabolite of retinol (vitamin A. In this new study, a total of 26 di- and mono-esters were screened to identify additional phthalate structures that disrupt the RSP and explore their mechanisms of action. The most potent PEs, those causing > 50% inhibition, contained aryl and cycloalkane groups or C4-C6 alkyl ester chains and were the same PEs reported to cause malformations in utero. They shared similar lipid solubility; logP values were between 4 and 6 and, except for PEs with butyl and phenyl groups, were stable for prolonged periods in culture. Mono- and cognate di-esters varied in ability to disrupt the RSP; e.g., DEHP was inactive but its monoester was active while DBuP was active yet its monoester was inactive. DBuP and dibenzyl phthalate both disrupted the synthesis of RA from retinol but not the ability of RA to activate gene transcription. Both PEs also disrupted the RSP in C3H10T1/2 multipotent mesenchymal stem cells. Based on this in vitro study showing that some PEs disrupt retinol signaling and previous in vivo studies that vitamin A/RA deficiency and PEs both cause strikingly similar anomalies in the male rat reproductive system, we propose that PE-mediated inhibition of testosterone and RA synthesis in utero are both causes of malformations in male rat offspring.

YCl3-Catalyzed Highly Selective Ring Opening of Epoxides by Amines at Room Temperature and under Solvent-Free Conditions

Directory of Open Access Journals (Sweden)

Wuttichai Natongchai

2017-11-01

Full Text Available A simple, efficient, and environmentally benign approach for the synthesis of β-amino alcohols is herein described. YCl3 efficiently carried out the ring opening of epoxides by amines to produce β-amino alcohols under solvent-free conditions at room temperature. This catalytic approach is very effective, with several aromatic and aliphatic oxiranes and amines. A mere 1 mol % concentration of YCl3 is enough to deliver β-amino alcohols in good to excellent yields with high regioselectivity.

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

Energy Technology Data Exchange (ETDEWEB)

Matasovic, Brunislav [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia); Bonifacic, Marija, E-mail: bonifacic@irb.h [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia)

2011-06-15

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals {sup {center_dot}C}O{sub 2}{sup -}, {sup {center_dot}C}H{sub 2}OH, {sup {center_dot}C}H(CH{sub 3})OH, and {sup {center_dot}C}H(CH{sub 3})O{sup -} have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production {sup 60}Co {gamma}-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U{sup {center_dot}} radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U{sup {center_dot}} radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of {alpha}-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism (). Thus, while both {sup {center_dot}C}H{sub 2}OH and {sup {center_dot}C}H(CH{sub 3})OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm{sup -3} concentrations, pH 7, brought about chain debromination to occur in the case of {sup {center_dot}C}H(CH{sub 3})OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of {alpha}-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U{sup {center_dot}} radicals have been estimated to amount to about {>=}85 and 1200 dm{sup 3} mol{sup -1} s{sup -1

Are bioassays useful tools to assess redox processes and biodegradation?

DEFF Research Database (Denmark)

Albrechtsen, Hans-Jørgen; Pedersen, Philip Grinder; Ludvigsen, L.

2002-01-01

sensitive hydrochemical or geochemical parameters, levels of hydrogen, and redox potential. However, all these approaches have to be evaluated against TEAP-bioassays as the most direct measure. We assessed successfully ongoing microbial-mediated redox processes by TEAP-bioassays in degradation studies...... of aromatic and chlorinated aliphatic compounds in landfill leachate plumes, and of pesticides in aquifers with various redox conditions....

Differences of diurnal variations of some aliphatic and polycyclic aromatic hydrocarbons concentrations in aerosols of the urban area of Madrid; Estudio de las variaciones diarias en las concentraciones de algunos hidrocarburos alifaticos y aromatico; policiclicos, en aerosoles de la zona urbana de Madrid

Energy Technology Data Exchange (ETDEWEB)

Perez, M. M.; Perez-Pastor, R. M.; Bea, F. J.; Campos, A.; Gonzalez, D.

1991-07-01

A study on daily concentration changes of polycyclic aromatic and aliphatic hydrocarbons (PAH's and AH's), was carried out in aerosols sampled m the Ciudad Universitaria of Madrid. Samples were taken at morning and night during February and June, for short sampling times, on glass fiber filters in Hi-Vol samplers, and then extracted ultrasonically with cyclohexane. Analysis were performed by HRGC with fused-silica capillary columns. The variable traffic rate, and the strong influence during winter periods of domestic heating are characteristic of this place. The aim of this work was to evaluate diurnal and seasonal variations of selected AH and PAH in the urban area of Madrid, by using descriptive parameters, such as total concentrations of AH and PAH, characteristic profiles and predominance carbon index. (Author)

Rhodium-catalyzed NH insertion of pyridyl carbenes derived from pyridotriazoles: a general and efficient approach to 2-picolylamines and imidazo[1,5-a]pyridines.

Science.gov (United States)

Shi, Yi; Gulevich, Anton V; Gevorgyan, Vladimir

2014-12-15

A general and efficient NH insertion reaction of rhodium pyridyl carbenes derived from pyridotriazoles was developed. Various NH-containing compounds, including amides, anilines, enamines, and aliphatic amines, smoothly underwent the NH insertion reaction to afford 2-picolylamine derivatives. The developed transformation was further utilized in a facile one-pot synthesis of imidazo[1,5-a]pyridines. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conversion characteristics of 10 selected oil shales

Energy Technology Data Exchange (ETDEWEB)

Miknis, F.P.

1989-08-01

The conversion behavior of 10 oil shale from seven foreign and three domestic deposits has been studied by combining solid- and liquid-state nuclear magnetic resonance (NMR) measurements with material balance Fischer assay conversion data. The extent of aromatization of aliphatic carbons was determined. Between zero and 42% of the raw shale aliphatic carbon formed aromatic carbon during Fischer assay. For three of the shales, there was more aromatic carbon in the residue after Fisher assay than in the raw shale. Between 10 and 20% of the raw shale aliphatic carbons ended up as aliphatic carbons on the spent shale. Good correlations were found between the raw shale aliphatic carbon and carbon in the oil and between the raw shale aromatic carbon and aromatic carbon on the spent shale. Simulated distillations and molecular weight determinations were performed on the shale oils. Greater than 50% of the oil consisted of the atmospheric and vacuum gas oil boiling fractions. 14 refs., 15 figs., 1 tab.

Bioassessment of bioremediation products in aquatic systems using cytotoxic and in vitro immune function assays

International Nuclear Information System (INIS)

Rice, C.D.; Roszell, L.E.

1995-01-01

Estuarine sediments and overlying water were collected from Back Bay Mississippi and placed in five 7.5 x 61 cm. glass-column mesocosms with a peristaltic recirculating system. Four columns received a sample of artificially weathered Louisiana Crude Oil spiked with either N + P, a PAH-metabolizing bacterial consortium collected in situ, or both. A fifth column excluded oil, bacteria, and nutrients. Aliphatic and aromatic fractions were extracted from each system and diluted in iso-octane. Poecoliopsis Hepatoma Cells (PLHC-1) and Rat Hepatoma Cells (H4IIE) were treated with 1/100--1/800 dilutions of each extract and protein synthesis, RNA synthesis, DNA synthesis, Cytochrome P4501A induction, and viability were determined. ∝-CD3 and ∝-IgM-stimulated proliferation of mouse lymphocytes, PWM-stimulated proliferation and PMA-stimulated oxidative burst activity of catfish lymphocytes and phagocytes, respective, were also determined. All extracts were overtly toxic to cell cultures compared to controls at a 1/100 dilution but only aliphatic fractions affected viability at higher dilutions. Aromatic fractions increased protein and RNA synthesis as well as induced P4501A at 1/400 and 1/800 dilutions. Fertilization with P + N increased toxic responses. Lymphocyte proliferation and fish phagocyte responses were more sensitive to aliphatic extracts. This approach may be useful for investigating the toxicity and biological impact of effluents

Comparison of the Photovoltaic Characteristics and Nanostructure of Fullerenes Blended with Conjugated Polymers with Siloxane-Terminated and Branched Aliphatic Side Chains

KAUST Repository

Kim, Do Hwan

2013-02-12

All-organic bulk heterojunction solar cells based on blends of conjugated polymers with fullerenes have recently surpassed the 8% efficiency mark and are well on their way to the industrially relevant ∼15% threshold. Using a low band-gap conjugated polymer, we have recently shown that polymer side chain engineering can lead to dramatic improvement in the in-plane charge carrier mobility. In this article, we investigate the effectiveness of siloxy side chain derivatization in controlling the photovoltaic performance of polymer:[6,6]-phenyl-C[71]-butyric acid methyl ester (PC71BM) blends and hence its influence on charge transport in the out-of-plane direction relevant for organic solar cells. We find that, in neat blends, the photocurrent of the polymer with siloxy side chains (PII2T-Si) is 4 times greater than that in blends using the polymer with branched aliphatic side chains (PII2T-ref). This difference is due to a larger out-of-plane hole mobility for PII2T-Si brought about by a largely face-on crystallite orientation as well as more optimal nanoscale polymer:PC71BM mixing. However, upon incorporating a common processing additive, 1,8-diiodooctane (DIO), into the spin-casting blend solution and following optimization, the PII2T-ref:PC71BM OPV device performance undergoes a large improvement and becomes the better-performing device, almost independent of DIO concentration (>1%). We find that the precise amount of DIO plays a larger role in determining the efficiency of PII2T-Si:PC71BM, and even at its maximum, the device performance lags behind optimized PII2T-ref:PC71BM blends. Using a combination of atomic force microscopy and small- and wide-angle X-ray scattering, we are able to elucidate the morphological modifications associated with the DIO-induced changes in both the nanoscale morphology and the molecular packing in blend films. © 2012 American Chemical Society.

Vitamin and amino acid auxotrophy in anaerobic consortia operating under methanogenic condition

OpenAIRE

Eiler, Alexander; Bertilsson, Stefan; Berry, David; Wendeberg, Anneli; Foght, Julia; Tan, Boonfei; Buck, Moritz; Hubalek, Valeria

2017-01-01

Syntrophy among Archaea and Bacteria facilitates the anaerobic degradation of organic compounds to CH4 and CO2. Particularly during aliphatic and aromatic hydrocarbon mineralization, as in crude oil reservoirs and petroleum contaminated sediments, metabolic interactions between obligate mutualistic microbial partners are of central importance1. Using micromanipulation combined with shotgun metagenomic approaches, we disentangled the genomes of complex consortia inside a short chain alkane deg...

Vitamin and Amino Acid Auxotrophy in Anaerobic Consortia Operating under Methanogenic Conditions

OpenAIRE

Valerie Hubalek; Moritz Buck; BoonFei Tan; Julia Foght; Annelie Wendeberg; David Berry; Stefan Bertilsson; Alexander Eiler; Karen G. Lloyd

2017-01-01

ABSTRACT Syntrophy among Archaea and Bacteria facilitates the anaerobic degradation of organic compounds to CH4 and CO2. Particularly during aliphatic and aromatic hydrocarbon mineralization, as in the case of crude oil reservoirs and petroleum-contaminated sediments, metabolic interactions between obligate mutualistic microbial partners are of central importance. Using micromanipulation combined with shotgun metagenomic approaches, we describe the genomes of complex consortia within short-ch...

Forms and Lability of Phosphorus in Algae and Aquatic Macrophytes Characterized by Solution 31P NMR Coupled with Enzymatic Hydrolysis

Science.gov (United States)

Feng, Weiying; Zhu, Yuanrong; Wu, Fengchang; He, Zhongqi; Zhang, Chen; Giesy, John P.

2016-11-01

Solution Phosphorus-31 nuclear magnetic resonance (31P NMR) spectroscopy coupled with enzymatic hydrolysis (EH) with commercially available phosphatases was used to characterize phosphorus (P) compounds in extracts of the dominant aquatic macrophytes and algae in a eutrophic lake. Total extractable organic P (Po) concentrations ranged from 504 to 1643 mg kg-1 and 2318 to 8395 mg kg-1 for aquatic macrophytes and algae, respectively. Using 31P NMR spectroscopy, 11 Po species were detected in the mono- and diester region. Additionally, orthophosphate, pyrophosphate and phosphonates were also detected. Using EH, phytate-like P was identified as the prevalent class of enzyme-labile Po, followed by labile monoester- and diester-P. Comparison of the NMR and EH data indicated that the distribution pattern of major P forms in the samples determined by the two methods was similar (r = 0.712, p < 0.05). Additional 31P NMR spectroscopic analysis of extracts following EH showed significant decreases in the monoester and pyrophosphate regions, with a corresponding increase in the orthophosphate signal, as compared to unhydrolyzed extracts. Based on these quantity and hydrolysis data, we proposed that recycling of Po in vegetative biomass residues is an important mechanism for long-term self-regulation of available P for algal blooming in eutrophic lakes.

A cold active (2R,3R)-(-)-di-O-benzoyl-tartrate hydrolyzing esterase from Rhodotorula mucilaginosa.

Science.gov (United States)

Zimmer, Christian; Platz, Tanja; Cadez, Neza; Giffhorn, Friedrich; Kohring, Gert-Wieland

2006-11-01

In a screening procedure a pink-colored yeast was isolated from enrichment cultures with (2R,3R)-(-)-di-O-benzoyl-tartrate (benzoyl-tartrate) as the sole carbon source. The organism saar1 was identified by morphological, physiological, and 18S ribosomal DNA/internal transcribed spacer analysis as Rhodotorula mucilaginosa, a basidiomycetous yeast. During growth the yeast hydrolyzed the dibenzoyl ester stoichiometrically to the monoester using the separated benzoate as the growth substrate, before the monoester was further cleaved into benzoate and tartrate, which were both metabolized. The corresponding benzoyl esterase was purified from the culture supernatant and characterized as a monomeric glycosylated 86-kDa protein with an optimum pH of 7.5 and an optimum temperature of 45 degrees C. At 0 degrees C the esterase still exhibited 20% of the corresponding activity at 30 degrees C, which correlates it to psychrophilic enzymes. The esterase could hydrolyze short chain p-nitrophenyl-alkyl esters and several benzoyl esters like benzoyl-methyl ester, ethylene-glycol-dibenzoyl ester, phenyl-benzoyl ester, cocaine, and 1,5-anhydro-D: -fructose-tribenzoyl ester. However feruloyl-ethyl ester was not hydrolyzed. The activity characteristics let the enzyme appear as a promising tool for synthesis of benzoylated compounds for pharmaceutical, cosmetic, or fine chemical applications, even at low temperatures.

Toxicity of jet fuel aliphatic and aromatic hydrocarbon mixtures on human epidermal Keratinocytes: evaluation based on in vitro cytotoxicity and interleukin-8 release

Energy Technology Data Exchange (ETDEWEB)

Yang, Jen-Hung (Chung-Shan Medical University Hospital, Department of Dermatology, Taichung, Taiwan, R.O.C); Lee, Chia-Hue; Tsang, Chau-Loong [National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan); Monteiro-Riviere, Nancy A.; Riviere, Jim E. [North Carolina State University, Center for Chemical Toxicology Research and Pharmacokinetics (CCTRP), Raleigh, NC (United States); Chou, Chi-Chung [National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan); National Chung-Hsing University, College of Veterinary Medicine, Taichung (Taiwan)

2006-08-15

Jet fuels are complex mixtures of aliphatic (ALI) and aromatic (ARO) hydrocarbons that vary significantly in individual cytotoxicity and proinflammatory activity in human epidermal keratinocytes (HEK). In order to delineate the toxicological interactions among individual hydrocarbons in a mixture and their contributions to cutaneous toxicity, nine ALI and five ARO hydrocarbons were each divided into five (high/medium/low cytotoxic and strong/weak IL-8 induction) groups and intra/inter-mixed to assess for their mixture effects on HEK mortality and IL-8 release. Addition of single hydrocarbon to JP-8 fuel was also evaluated for their changes in fuel dermatotoxicity. The results indicated that when hydrocarbons were mixed, HEK mortality and IL-8 release were not all predictable by their individual ability affecting these two parameters. The lowest HEK mortality (7%) and the highest IL-8 production were induced with mixtures including high cytotoxic and weak IL-8 inductive ARO hydrocarbons. Antagonistic reactions not consistently correlated with ALI carbon chain length and ARO structure were evident and carried different weight in the overall mixture toxicities. Single addition of benzene, toluene, xylene or ethylbenzene for up to tenfold in JP-8 did not increase HEK mortality while single addition of ALI hydrocarbons exhibited dose-related differential response in IL-8. In an all ALI environment, no single hydrocarbon is the dominating factor in the determination of HEK cytotoxicity while deletion of hexadecane resulted in a 2.5-fold increase in IL-8 production. Overall, decane, undecane and dodecane were the major hydrocarbons associated with high cytotoxicity while tetradecane, pentadecane and hexadecane were those which had the greatest buffering effect attenuating dermatotoxicity. The mixture effects must be considered when evaluating jet fuel toxicity to HEK. (orig.)

Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Liu, Shasha [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhu, Yuanrong, E-mail: zhuyuanrong07@mails.ucas.ac.cn [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Meng, Wei, E-mail: mengwei@craes.org.cn [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); He, Zhongqi [USDA-ARS Southern Regional Research Center, 1100 Robert E Lee Blvd, New Orleans, LA 70124 (United States); Feng, Weiying [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhang, Chen [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Giesy, John P. [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Department of Biomedical and Veterinary Biosciences and Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan (Canada)

2016-02-01

Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O–C–O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH{sub 3} and COO/N–C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH{sub 3} and COO/N–C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. - Highlights: • WEOM derived from aquatic macrophytes was characterized. • C and P in WEOM were characterized by solid {sup 13}C NMR and solution {sup 31}P NMR. • Degradation and transformation of macrophyte-derived C and P were investigated. • Macrophyte-derived WEOM are important source for bioavailable nutrients in lakes.

Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state 13C NMR and solution 31P NMR spectroscopy

International Nuclear Information System (INIS)

Liu, Shasha; Zhu, Yuanrong; Meng, Wei; He, Zhongqi; Feng, Weiying; Zhang, Chen; Giesy, John P.

2016-01-01

Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state 13 C NMR and solution 31 P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O–C–O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH 3 and COO/N–C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH 3 and COO/N–C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. - Highlights: • WEOM derived from aquatic macrophytes was characterized. • C and P in WEOM were characterized by solid 13 C NMR and solution 31 P NMR. • Degradation and transformation of macrophyte-derived C and P were investigated. • Macrophyte-derived WEOM are important source for bioavailable nutrients in lakes.

QTL list: [PGDBj Registered plant list, Marker list, QTL list, Plant DB link and Genome analysis methods[Archive

Lifescience Database Archive (English)

Full Text Available QT84691 Brassica oleracea Brassicaceae ... Flower buds_Aliphatic glucosinolates (Aliphatic) Glucosinolate Synt...hesis 4 ... LG_03 ... 100 5.3 ... 10.1371/journal.pone.0091428 24614913

Improvement of brassica oilseeds through modern biotechnological approaches

International Nuclear Information System (INIS)

Khan, M.R.; Rashid, H.

2007-01-01

Pakistan is chronically deficient in the production of edible oils. So much so that 3/4 (three fourth) of the country's requirements are met through imports, costing huge amounts in foreign exchange. The total edible-oil requirements of Pakistan for 1999-2000 stands at 2 million tons. The rest was imported on heavy foreign exchange cost of US dollars 800 million/year (Anonymous, 2000). One disturbing aspect of this critical issue is an annual increase in the gap between consumption and domestic production of edible oils. The different uses of rapeseed have given rise to specialized cultivars, and it is important to differentiate between the three principal types viz. seed quality, high erucic acid (HEAR), and canola. The term Canola refers to seed or seed-products with less than 2% erucic acid in the oil and less than 30 macro mol/g meal of aliphatic glucosinolates. (author)

Carotenoids of Red, Brown, and Black Specimens of Plectropomus leopardus, the Coral Trout (Suziara in Japanese).

Science.gov (United States)

Maoka, Takashi; Sato, Wataru; Nagai, Hidetada; Takahashi, Toshiyuki

2017-06-01

This study investigated the carotenoids occurring in the integument of Plectropomus leopardus, the coral trout. For a red specimen, the major carotenoids included astaxanthin diester and monoester, as well as α-cryptoxanthin ester, tunaxanthin diester, adonixanthin diester, adonirubin ester, and adonirubin; for brown and black specimens, tunaxanthin diester was the main carotenoid. 1 H-NMR and MS spectral analyses showed that docosahexaenoic acid was the sole fatty acid esterified with xanthophylls in the coral trout.

VISCOSITY OF BINARY NON-ELECTROLYTE LIQUID MIXTURES: PREDICTION AND CORRELATION

Directory of Open Access Journals (Sweden)

Mirjana Lj. Kijevčanin

2008-11-01

Full Text Available The viscosity of 31 binary liquid mixtures containing diverse groups of organic compounds, determined at atmospheric pressure: alcohols, alkanes (cyclo and aliphatic, esters, aromatics, ketones etc., were calculated using two different approaches, correlative (with Teja-Rice and McAllister models and predictive by group contribution models (UNIFAC-VISCO, ASOG-VISCO and Grunberg-Nissan. The obtained results were analysed in terms of the applied approach and model, the structure of the investigated mixtures, the nature of components of the mixtures and the influence of alkyl chain length of the alcohol molecule.

QTL list: [PGDBj Registered plant list, Marker list, QTL list, Plant DB link and Genome analysis methods[Archive

Lifescience Database Archive (English)

Full Text Available QT84688 Brassica oleracea Brassicaceae ... Flower buds_Aliphatic glucosinolates (Aliphatic) Glucosinolate Synt...hesis 4 fito375 LG_02 ... 90 7.1 ... 10.1371/journal.pone.0091428 24614913

Biodegradation of polyester. Polyester no bunkai sei

Energy Technology Data Exchange (ETDEWEB)

Tokiwa, Y. (Agency of Industrial Science and Technology, Tokyo (Japan). Fermentation Research Inst.)

1991-09-10

Penicillium sp. 14-3 and penicillium sp. 26-1 can degrade various kinds of polyester. The results of studies made on hydrolysis of polyester by enzyme, hydrolysis of polyester by various kinds of lipase, and degradation of ester type polyurethane by microbes and lipase are introduced. For the improvement of physical properties of aliphatic polyester, aromatic-aliphatic polyester copolymers (CPE) have been synthesized to study the biodegradability. Copolymer in which a number of polyamide (nylon) are alternately introduced (CPAE) to aliphatic polyester has been developed. The result of studies made on the degradability of a blended body of PCL and natural high polymer, and on the collapsibility by lipase of high polymer materials including aliphatic polyamide are introduced. 26 refs., 5 figs., 1 tab.

Absorbable and biodegradable polymers

CERN Document Server

Shalaby, Shalaby W

2003-01-01

INTRODUCTION NOTES: Absorbable/Biodegradable Polymers: Technology Evolution. DEVELOPMENT AND APPLICATIONOF NEW SYSTEMS: Segmented Copolyesters with Prolonged Strength Retention Profiles. Polyaxial Crystalline Fiber-Forming Copolyester. Polyethylene Glycol-Based Copolyesters. Cyanoacrylate-Based Systems as Tissue Adhesives. Chitosan-Based Systems. Hyaluronic Acid-Based Systems. DEVELOPMENTS IN PREPARATIVE, PROCESSING, AND EVALUATION METHODS: New Approaches to the Synthesis of Crystalline. Fiber-Forming Aliphatic Copolyesters. Advances in Morphological Development to Tailor the Performance of Me

Ultrasmall Peptides Self-Assemble into Diverse Nanostructures: Morphological Evaluation and Potential Implications

Directory of Open Access Journals (Sweden)

Charlotte A.E. Hauser

2011-09-01

Full Text Available In this study, we perform a morphological evaluation of the diverse nanostructures formed by varying concentration and amino acid sequence of a unique class of ultrasmall self-assembling peptides. We modified these peptides by replacing the aliphatic amino acid at the C-aliphatic terminus with different aromatic amino acids. We tracked the effect of introducing aromatic residues on self-assembly and morphology of resulting nanostructures. Whereas aliphatic peptides formed long, helical fibers that entangle into meshes and entrap >99.9% water, the modified peptides contrastingly formed short, straight fibers with a flat morphology. No helical fibers were observed for the modified peptides. For the aliphatic peptides at low concentrations, different supramolecular assemblies such as hollow nanospheres and membrane blebs were found. Since the ultrasmall peptides are made of simple, aliphatic amino acids, considered to have existed in the primordial soup, study of these supramolecular assemblies could be relevant to understanding chemical evolution leading to the origin of life on Earth. In particular, we propose a variety of potential applications in bioengineering and nanotechnology for the diverse self-assembled nanostructures.

Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates and 3d-Block Metal Counterions.

Science.gov (United States)

Thuéry, Pierre; Harrowfield, Jack

2016-03-07

Twelve new complexes were obtained from reaction of uranyl ions with the aliphatic dicarboxylic acids HOOC-(CH2)n-2-COOH (H2Cn; n = 7-10 and 12) under solvo-hydrothermal conditions, in the presence of 3d-block metal ions (Mn(2+), Fe(3+), Co(2+), Ni(2+), and Cu(2+)) and 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen). In contrast to previously reported triple-stranded helicates obtained with C9(2-) and C12(2-), all these complexes crystallize as polymeric one-dimensional (1D) or two-dimensional (2D) species. [Fe(bipy)3][(UO2)2(C7)3]·3H2O (1), [Cu(phen)2]2[(UO2)3(C7)4(H2O)2]·2H2O (2), and [Cu(bipy)2]2[(UO2)2(C9)3] (6), in which the 3d cation was reduced in situ, are 1D ladderlike polymers displaying tetra- or hexanuclear rings, of sufficient width to encompass two counterions in 2 and 6. The three complexes [Co(phen)3][(UO2)3(C8)3(O)]·H2O (3), [Ni(phen)3][(UO2)3(C8)3(O)]·H2O (4) and [Co(phen)3][(UO2)3(C9)3(O)]·H2O (5) contain bis(μ3-oxo)-bridged tetranuclear secondary building units, and they crystallize as deeply furrowed 2D assemblies. Depending on the nature of the counterion, C10(2-) gives [Ni(bipy)3][(UO2)2(C10)3]·2H2O (7), a 2D network displaying elongated decanuclear rings containing the counterions, or [Mn(phen)3][(UO2)2(C10)3]·6H2O (8), [Co(phen)3][(UO2)2(C10)3]·7H2O (9), and [Ni(phen)3][(UO2)2(C10)3]·7H2O (10), which consist of 2D assemblies with honeycomb topology; the hexanuclear rings in 8-10 are chairlike and occupied by one counterion and two uranyl groups from neighboring layers. Two complexes of the ligand with the longest chain, C12(2-), are reported. [UO2(C12)(bipy)] (11) is a neutral 1D species in which bipy chelates the uranyl ion and plays an important role in the packing through π-stacking interactions. Two polymeric units, 1D and 2D, coexist in the complex [Ni(bipy)3][(UO2)2(C12)3][UO2(C12)(H2O)2]·H2O (12); the 2D network has the honeycomb topology, but the hexanuclear rings are markedly convoluted, with local features akin to

Determination of aliphatic amines in mineral flotation liquors and reagents by high-performance liquid chromatography after derivatization with 4-chloro-7-nitrobenzofurazan.

Science.gov (United States)

Hao, F; Lwin, T; Bruckard, W J; Woodcock, J T

2004-11-05

The method described here fulfils the need for a suitable analytical method to determine the concentrations of single and mixed aliphatic amines in the range from hexylamine (C6) to octadecylamine (C18) in flotation test solutions and in commercial flotation collectors. Amines do not have a UV-vis spectrum in aqueous solution but by reacting an amine-containing solution with 4-chloro-7-nitrobenzofurazan solution (chloro-NBD), derivatized products (amino-NBDs) are formed which have absorbance maxima at 470nm. Excess chloro-NBD and the amino-NBDs can be separated from each other by high-performance liquid chromatography (HPLC) and their concentrations measured with a UV-vis detector. Important variables in the derivatization stage are pH, temperature, chloro-NBD concentration, and reaction time, all of which interact with each other. A three-stage statistical procedure was used to determine the optimum conditions. In each stage, an 8-test design was used in which a high and low limit was set for each variable, and the chromatogram peak area of the derived amino-NBD was measured. The optimum derivatization conditions established were pH 8.9, chloro-NBD concentration 0.20% (w/v), temperature 70 degrees C, and reaction time 60 min. Optimum elution conditions for chromatography were an eluent containing 80% (v/v) acetonitrile in aqueous solution containing 40mM acetic acid at pH 4.5. With a flow rate of 2.0 ml/min, dodecylamine had a retention time of about 3 min, whereas octadecylamine had a retention time of 44 min. Straight-line calibration curves were obtained up to at least 200 ppm of amine in solution. The lower limit of detection was estimated to be 0.05 microM (10ppb) with a signal to noise ratio of 3. No interfering substances were found. The method was successfully applied to the analysis of solutions from an actual flotation test and to a solid commercial amine.

QTL list: [PGDBj Registered plant list, Marker list, QTL list, Plant DB link and Genome analysis methods[Archive

Lifescience Database Archive (English)

Full Text Available QT84692 Brassica oleracea Brassicaceae ... Flower buds_Aliphatic glucosinolates (Aliphatic) Glucosinolate Synt...hesis 4 BRMS042, BRMS050 LG_07 ... 43 20.3 ... 10.1371/journal.pone.0091428 24614913

QTL list: [PGDBj Registered plant list, Marker list, QTL list, Plant DB link and Genome analysis methods[Archive

Lifescience Database Archive (English)

Full Text Available thesis 4 pW125dE LG_03 ... 46 3.3 ... 10.1371/journal.pone.0091428 24614913 ... QT84689 Brassica oleracea Brassicaceae ... Flower buds_Aliphatic glucosinolates (Aliphatic ) Glucosinolate Syn

Organic geochemistry of deep ground waters from the Palo Duro Basin, Texas: implications for radionuclide complexation, ground-water origin, and petroleum exploration

International Nuclear Information System (INIS)

Means, J.L.; Hubbard, N.J.

1985-05-01

This report describes the organic geochemistry of 11 ground-water samples from the Palo Duro Basin, Texas and discusses the implications of their organic geochemical compositions in terms of radionuclide complexation, ground-water origin, and the petroleum potential of two candidate repository sites in Deaf Smith and Swisher Counties. Short-chain aliphatic acid anions are the principal organic constituents present. Stability constant data and simple chemical equilibria calculations suggest that short-chain aliphatic acids are relatively weak complexing agents. The extent of complexation of a typical actinide by selected inorganic ligands present in these brines is expected to far outweigh actinide complexation by the aliphatic acid anions. Various lines of evidence suggest that some portion of the bromide concentrations in the brines is derived from the same source as the short-chain aliphatic acid anions. When the postulated organic components are subtracted from total bromide concentrations, the origins of the Palo Duro brines, based on chloride versus bromide relationships, appear largely consistent with origins based on isotopic evidence. The short-chain aliphatic acid anion content of the Palo Duro brines is postulated to have been much greater in the geologic past. Aliphatic acid anions are but one of numerous petroleum proximity indicators, which consistently suggest a greater petroleum exploration potential for the area surrounding the Swisher County site than the region encompassing the candidate site in Deaf Smith County. Short-chain aliphatic acid anions appear to provide a useful petroleum exploration tool as long as the complex reactions that may dimish their concentrations in ground water are recognized. 71 refs., 10 figs., 10 tabs

Structural Evolution of Kerogen and Bitumen during Thermal Maturation examined by Fourier-Transform Infrared Spectroscopy

Science.gov (United States)

Craddock, P. R.; Le Doan, T. V.; Pomerantz, A.

2014-12-01

Kerogen—the organic matter that is solid and insoluble in organic solvents—is a key component of organic-rich mudstones. The composition of kerogen affects the storage and transport of hydrocarbons in these unconventional resources and is known to change with thermal maturity. We report here using FTIR spectroscopy, the compositional characteristics of kerogen as a function of thermal maturity, together with the compositional characteristics of the organic phase, bitumen—the organic matter that is solid, but soluble in organic solvents. Kerogen is consumed during thermal maturation, whereas bitumen is an intermediary formed at low maturity from kerogen and consumed at higher maturities in formation of oil and gas. Bitumen relative to kerogen has higher aliphatic content, lower aromatic content, and lower abundance of oxygenated functions. At low maturity (vitrinite reflectance equivalent VRe ~ 0.5-0.9 %), the average length of aliphatic chains in bitumen increases during bitumen formation. At higher thermal maturities (VRe > 1.0-1.3 %), average aliphatic chain length decreases as bitumen is consumed. This evolution contrasts to that in kerogen, where aliphatic chain lengths shorten during all stages of maturation. Breakdown of kerogen appears to be driven by cleavage of oxygen functions at low maturity and removal of aliphatic carbons at higher maturities. These aliphatic-rich fragments may comprise the bitumen, and may in part explain the solubility of bitumen in organic solvents. Bitumen shows evidence of oxidation at low thermal maturity, a phenonemom not documented for kerogen. Bitumen maturation and degradation at higher thermal maturity is driven by cleavage and loss of aliphatic carbons, and is coincident with the maximum generation of oil and gas. The aromatic content of bitumen and of kerogen both increase during maturation as a consequence of the loss of aliphatic carbon. The oil and gas generation potential of the residual organic matter thus

Hardening by means of ionising radiation

International Nuclear Information System (INIS)

Spoor, H.; Demmler, K.

1979-01-01

The polymerisable ethylic unsaturated mixture can be hardened by means of electron irradiation and used as a corrosion preventive layer. The mixture mainly consists of at least a di-olefinic unsaturated polyester, partial esters of polycarbonic acids, in particular the monoester of dicarbonic acids, with a copolymerizable C-C double bond, and mono-olefine unsaturated hydrocarbons, for example vinyl aromatics. The coatings exhibit good adhesion to the substrate, in particular to metal, and good flexibility. (DG) [de

Transplacental transfer of monomethyl phthalate and mono(2-ethylhexyl) phthalate in a human placenta perfusion system

DEFF Research Database (Denmark)

Mose, Tina; Knudsen, Lisbeth E; Hedegaard, Morten

2007-01-01

The transplacental passage of monomethylphtalate (mMP) and mono (2-ethylhexyl) phthalate (mEHP) was studied using an ex vivo placental perfusion model with simultaneous perfusion of fetal and maternal circulation in a single cotyledon. Umbilical cord blood and placental tissue collected both before...... plasma samples. mMP and possibly other short-chained phthalate monoesters in maternal blood can cross the placenta by slow transfer, whereas the results indicate no placental transfer of mEHP. Further studies are recommended....

Synthesis and Characterization of Polycarbonates by Melt Phase Interchange Reactions of Alkylene and Arylene Diacetates with Alkylene and Arylene Diphenyl Dicarbonates

Directory of Open Access Journals (Sweden)

Bassam A. Sweileh

2010-05-01

Full Text Available This work presents a new synthetic approach to aromatic and aliphatic polycarbonates by melt polycondensation of bisphenol A diacetates with alkylene- and arylenediphenyl dicarbonates. The diphenyl dicarbonates were prepared from phenyl chloroformate and the corresponding dihydroxy compounds. The process involved a precondensation step under a slow stream of dry argon with the elimination of phenyl acetate, followed by melt polycondensation at high temperature and under vacuum. The potential of this reaction is demonstrated by the successful synthesis of a series of aromatic-aromatic and aromatic-aliphatic polycarbonates having inherent viscosities from 0.19 to 0.43 dL/g. Thus low to intermediate molecular mass polymers were obtained. The 13C-NMR spectra of the carbon of the carbonate group showed that the formed polycarbonates contain partial random sequence distribution of monomer residues in their chains. The polycarbonates were characterized by inherent viscosity, FTIR, 1H-NMR and 13C-NMR spectroscopy. The glass transition temperatures, measured by DSC, of the polycarbonates were in the range 13–108 ºC. The thermogravimetric curves of showed that these polymers have good thermal stability up to 250 ºC. The present approach may open the door for novel polycarbonates containing other organic functional groups.

Degradation and structure change of humic acids corresponding to water decline in Zoige peatland, Qinghai-Tibet Plateau

Energy Technology Data Exchange (ETDEWEB)

Guo, Xuejun, E-mail: guoxj21@yahoo.com.cn; Du, Wei; Wang, Xuan; Yang, Zhifeng, E-mail: zfyang@bnu.edu.cn

2013-02-15

As the largest plateau-type wetland in the world and the largest peat storage in China, Zoige wetland faces severe water decline, and consequently accelerated peat degradation and carbon emission. Here, a variety of characterization approaches, including elemental analysis, UV–vis spectra, FT-IR spectra, and solid state {sup 13}C NMR spectra were used to investigate the degradation and the structural shift of humic acids (HAs) in correspondence with serious water loss in Zoige peatland. Water loss derived from both natural slope and artificial drainage caused a substantial degradation of organic matter and HAs. Compared with the blocks immersed by free surface water, HAs extracted from the drier blocks had more pronounced signals of carboxyl and carbonyl groups, but carried lower content of methoxyl, carbohydrate, alcohol and ether groups. The total aliphatic carbon in HAs from natural-slope drier site decreased almost one half, but in the artificial-drained site, only slightly decreased. Correspondingly, the HA aromaticity substantially increased in the site undergoing the longer time of aerobic oxidation, whereas varied little in the site impacted by extensive water leaching. - Highlights: ► HAs were decomposed significantly due to water loss in Zoige peatland. ► Water loss induced a significant shift in FT-IR and {sup 13}C NMR spectra of HAs. ► The ratio of aliphatic to O-aliphatic carbon (A/O-A ratio) dramatically increased. ► The aromaticity of HAs increased with water loss in the higher-altitude site.

Degradation and structure change of humic acids corresponding to water decline in Zoige peatland, Qinghai-Tibet Plateau

International Nuclear Information System (INIS)

Guo, Xuejun; Du, Wei; Wang, Xuan; Yang, Zhifeng

2013-01-01

As the largest plateau-type wetland in the world and the largest peat storage in China, Zoige wetland faces severe water decline, and consequently accelerated peat degradation and carbon emission. Here, a variety of characterization approaches, including elemental analysis, UV–vis spectra, FT-IR spectra, and solid state 13 C NMR spectra were used to investigate the degradation and the structural shift of humic acids (HAs) in correspondence with serious water loss in Zoige peatland. Water loss derived from both natural slope and artificial drainage caused a substantial degradation of organic matter and HAs. Compared with the blocks immersed by free surface water, HAs extracted from the drier blocks had more pronounced signals of carboxyl and carbonyl groups, but carried lower content of methoxyl, carbohydrate, alcohol and ether groups. The total aliphatic carbon in HAs from natural-slope drier site decreased almost one half, but in the artificial-drained site, only slightly decreased. Correspondingly, the HA aromaticity substantially increased in the site undergoing the longer time of aerobic oxidation, whereas varied little in the site impacted by extensive water leaching. - Highlights: ► HAs were decomposed significantly due to water loss in Zoige peatland. ► Water loss induced a significant shift in FT-IR and 13 C NMR spectra of HAs. ► The ratio of aliphatic to O-aliphatic carbon (A/O-A ratio) dramatically increased. ► The aromaticity of HAs increased with water loss in the higher-altitude site

A new, direct analytical method using LC-MS/MS for fatty acid esters of 3-chloro-1,2-propanediol (3-MCPD esters) in edible oils.

Science.gov (United States)

Yamazaki, K; Ogiso, M; Isagawa, S; Urushiyama, T; Ukena, T; Kibune, N

2013-01-01

A new, direct analytical method for the determination of 3-chloro-1,2-propanediol fatty acid esters (3-MCPD esters) was developed. The targeted 3-MCPD esters included five types of monoester and 25 [corrected] types of diester. Samples (oils and fats) were dissolved in a mixture of tert-butyl methyl ether and ethyl acetate (4:1), purified using two solid-phase extraction (SPE) cartridges (C(18) and silica), then analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Five monoesters and five diesters with the same fatty acid group could be separated and quantified. Pairs of 3-MCPD diesters carrying the same two different fatty acid groups, but at reversed positions (sn-1 and sn-2), could not be separated and so were expressed as a sum of both compounds. The limits of quantification (LOQs) were estimated to be between 0.02 to 0.08 mg kg(-1), depending on the types of 3-MCPD ester. Repeatability expressed as relative standard deviation (RSD(r)%) varied from 5.5% to 25.5%. The new method was shown to be applicable to various commercial edible oils and showed levels of 3-MCPD esters varying from 0.58 to 25.35 mg kg(-1). The levels of mono- and diesters ranged from 0.10 to 0.69 mg kg(-1) and from 0.06 to 16 mg kg(-1), respectively.

Biodegradation of phthalic acid esters (PAEs) and in silico structural characterization of mono-2-ethylhexyl phthalate (MEHP) hydrolase on the basis of close structural homolog.

Science.gov (United States)

Singh, Neha; Dalal, Vikram; Mahto, Jai Krishna; Kumar, Pravindra

2017-09-15

Three bacterial strains capable of degrading phthalates namely Pseudomonas sp. PKDM2, Pseudomonas sp. PKDE1 and Pseudomonas sp. PKDE2 were isolated and characterized for their degradative potential. These strains efficiently degraded 77.4%-84.4% of DMP, 75.0%-75.7% of DEP and 71.7%-74.7% of DEHP, initial amount of each phthalate is 500mgL -1 of each phthalate, after 44h of incubation. GC-MS results reveal the tentative DEHP degradation pathway, where hydrolases mediate the breakdown of DEHP to phthalic acid (PA) via an intermediate MEHP. MEHP hydrolase is a serine hydrolase which is involved in the reduction of the MEHP to PA. The predicted 3D model of MEHP hydrolase from Pseudomonas mosselii was docked with phthalate monoesters (PMEs) such as MEHP, mono-n-hexyl phthalate (MHP), mono-n-butyl phthalate (MBP) and mono-n-ethyl phthalate (MEP), respectively. Docking results show the distance between the carbonyl carbon of respective phthalate monoester and the hydroxyl group of catalytic serine lies in the range of 2.9 to 3.3Å, which is similar to the ES complex of other serine hydrolases. This structural study highlights the interaction and the role of catalytic residues of MEHP hydrolase involved in the biodegradation of PMEs to phthalate. Copyright © 2017 Elsevier B.V. All rights reserved.

Stability and changes in astaxanthin ester composition from Haematococcus pluvialis during storage

Science.gov (United States)

Miao, Fengping; Geng, Yahong; Lu, Dayan; Zuo, Jincheng; Li, Yeguang

2013-11-01

In this paper, we investigated the effects of temperature, oxygen, antioxidants, and corn germ oil on the stability of astaxanthin from Haematococcus pluvialis under different storage conditions, and changes in the composition of astaxanthin esters during storage using high performance liquid chromatography and spectrophotometry. Oxygen and high temperatures (22-25°C) significantly reduced the stability of astaxanthin esters. Corn germ oil and antioxidants (ascorbic acid and vitamin E) failed to protect astaxanthin from oxidation, and actually significantly increased the instability of astaxanthin. A change in the relative composition of astaxanthin esters was observed after 96 weeks of long-term storage. During storage, the relative amounts of free astaxanthin and astaxanthin monoesters declined, while the relative amount of astaxanthin diesters increased. Thus, the ratio of astaxanthin diester to monoester increased, and this ratio could be used to indicate if astaxanthin esters have been properly preserved. If the ratio is greater than 0.2, it suggests that the decrease in astaxanthin content could be higher than 20%. Our results show that storing algal powder from H. pluvialis or other natural astaxanthin products under vacuum and in the dark below 4°C is the most economical and applicable storage method for the large-scale production of astaxanthin from H. pluvialis. This storage method can produce an astaxanthin preservation rate of at least 80% after 96 weeks of storage.

Kinetics of organic matter degradation in the Murchison meteorite for the evaluation of parent-body temperature history

Science.gov (United States)

Kebukawa, Yoko; Nakashima, Satoru; Zolensky, Michael E.

2010-01-01

To evaluate kinetic parameters for thermal degradation of organic matter, in situ heating experiments of insoluble organic matter (IOM) and bulk of Murchison (CM2) meteorite were conducted under Fourier transform infrared micro-spectroscopy combined with a heating stage. Decreases of aliphatic C-H band area under Ar flow were well fitted with Ginstling-Brounshtein three-dimensional diffusion model, and the rate constants for decreases of aliphatic C-H were determined. Activation energies Ea and frequency factors A obtained from these rate constants at different temperatures using the Arrhenius equation were Ea=109+/-3kJmol-1 and A=8.7×104s-1 for IOM, and Ea=61+/-6kJmol-1 and A=3.8s-1 for bulk, respectively. Activation energy values of aliphatic C-H decrease are larger for IOM than bulk. Hence, the mineral assemblage of the Murchison meteorite might have catalytic effects for the organic matter degradation. Using obtained kinetic expressions, the time scale for metamorphism can be estimated for a given temperature with aliphatic C-H band area, or the temperature of metamorphism can be estimated for a given time scale. For example, using the obtained kinetic parameters of IOM, aliphatic C-H is lost approximately within 200years at 100°C and 100Myr at 0°C. Assuming alteration period of 7.5Myr, alteration temperatures could be calculated to be <15+/-12°C. Aliphatic C-H decrease profiles in a parent body can be estimated using time-temperature history model. The kinetic expression obtained by the infrared spectral band of aliphatic C-H could be used as an alternative method to evaluate thermal processes of organic matter in carbonaceous chondrites.

Evaluation of certain food additives.

Science.gov (United States)

2012-01-01

This report represents the conclusions of a Joint FAO/WHO Expert Committee convened to evaluate the safety of various food additives, including flavouring agents, with a view to concluding as to safety concerns and to preparing specifications for identity and purity. The first part of the report contains a general discussion of the principles governing the toxicological evaluation of and assessment of dietary exposure to food additives, including flavouring agents. A summary follows of the Committee's evaluations of technical, toxicological and dietary exposure data for five food additives (magnesium dihydrogen diphosphate; mineral oil (medium and low viscosity) classes II and III; 3-phytase from Aspergillus niger expressed in Aspergillus niger; serine protease (chymotrypsin) from Nocardiopsis prasina expressed in Bacillus licheniformis; and serine protease (trypsin) from Fusarium oxysporum expressed in Fusarium venenatum) and 16 groups of flavouring agents (aliphatic and aromatic amines and amides; aliphatic and aromatic ethers; aliphatic hydrocarbons, alcohols, aldehydes, ketones, carboxylic acids and related esters, sulfides, disulfides and ethers containing furan substitution; aliphatic linear alpha,beta-unsaturated aldehydes, acids and related alcohols, acetals and esters; amino acids and related substances; epoxides; furfuryl alcohol and related substances; linear and branched-chain aliphatic, unsaturated, unconjugated alcohols, aldehydes, acids and related esters; miscellaneous nitrogen-containing substances; phenol and phenol derivatives; pyrazine derivatives; pyridine, pyrrole and quinoline derivatives; saturated aliphatic acyclic branched-chain primary alcohols, aldehydes and acids; simple aliphatic and aromatic sulfides and thiols; sulfur-containing heterocyclic compounds; and sulfur-substituted furan derivatives). Specifications for the following food additives were revised: ethyl cellulose, mineral oil (medium viscosity), modified starches and titanium

Carcinostatic effects of diverse ascorbate derivatives in comparison with aliphatic chain moiety structures: Promotion by combined hyperthermia and reduced cytotoxicity to normal cells.

Science.gov (United States)

Asada, Ryoko; Kageyama, Katsuhiro; Tanaka, Hiroshi; Kimura, Masatugu; Saitoh, Yasukazu; Miwa, Nobuhiko

2012-05-01

In this study, using human tongue squamous carcinoma cells (HSC-4) carcinostatic activity was compared for diverse L-ascorbic acid (Asc) derivatives, including the 'straight-C(16)-chain types', 6-O-palmitoyl-Asc (A6-P) and Asc-2-phosphate-6-O-palmitate sodium salt (APPS), as well as the 'branched-C(16)-chain types', Asc-2-phosphate-6-O-(2'-hexyl)decanoate (APHD), an isomer of APPS, and Asc-2,3,5,6-O-tetra-(2'-hexyl)decanoate (VCIP). The order of magnitude of the carcinostatic effects at 37°C was: APPS>A6-P = APHD>VCIP and at 42°C was APPS = A6-P>APHD>VCIP. Therefore, the two straight-C(16)-chain derivatives, APPS and A6-P, had a greater effect compared to the two branched-C(16)-chain Asc derivatives, which are considered to have more difficulty with 'orientation along cell-membrane-glycerolipid direction'. APPS-treated HCS-4 cells were observed for a decrease in cell number, cell shrinkage, pycnosis indicative of apoptosis and cell deformation. The order of cytotoxicity for the normal human dermal fibroblasts (OUMS-36) at 37°C was: A6-P (50% inhibitory concentration: 150-300 μM)>APHD (450-600 μM)>Asc = APPS (800-1000 μM). Accordingly, APHD was more cytotoxic than APPS, since the straight-C(16)-chain type, which was eliminated after the enzymatic esterolysis of APPS, is metabolized via the 'fatty acid β-oxidation cycle' more efficiently in normal cells. Thus, APPS had a greater advantage over APHD, A6-P and VCIP in terms of carcinostatic effects at 37°C, carcinostasis promotion at 42°C and a decrease of cytotoxicity to normal cells. This observation suggests a marked potential for aliphatic chain-moiety structures as anticancer agents, due to their cancer-selective carcinostasis and combined efficacy with hyperthermia, without causing side effects.

Novel biodegradable aliphatic poly(butylene succinate-co-cyclic carbonate)s bearing functionalizable carbonate building blocks: II. Enzymatic biodegradation and in vitro biocompatibility assay.

Science.gov (United States)

Yang, Jing; Tian, Weisheng; Li, Qiaobo; Li, Yang; Cao, Amin

2004-01-01

In a previous study, we have reported chemical synthesis of novel aliphatic poly(butylene succinate-co-cyclic carbonate) P(BS-co-CC)s bearing various functionalizable carbonate building blocks, and this work will continue to present our new studies on their enzymatic degradation and in vitro cell biocompatibility assay. First, enzymatic degradation of the novel P(BS-co-CC) film samples was investigated with two enzymes of lipase B Candida Antartic (Novozyme 435) and lipase Porcine Pancreas PPL, and it was revealed that copolymerizing linear poly(butylene succinate) PBS with a functionalizable carbonate building block could remarkably accelerate the enzymatic degradation of a synthesized product P(BS-co-CC), and its biodegradation behavior was found to strongly depend on the overall impacts of several important factors as the cyclic carbonate (CC) comonomer structure and molar content, molar mass, thermal characteristics, morphology, the enzyme-substrate specificity, and so forth. Further, the biodegraded residual film samples and water-soluble enzymatic degradation products were allowed to be analyzed by means of proton nuclear magnetic resonance (1H NMR), gel permeation chromatograph (GPC), differential scanning calorimeter (DSC), attenuated total reflection FTIR (ATR-FTIR), scanning electron microscope (SEM), and liquid chromatograph-mass spectrometry (LC-MS). On the experimental evidences, an exo-type mechanism of enzymatic chain hydrolysis preferentially occurring in the noncrystalline domains was suggested for the synthesized new P(BS-co-CC) film samples. With regard to their cell biocompatibilities, an assay with NIH 3T3 mouse fibroblast cell was conducted using the novel synthesized P(BS-co-CC) films as substrates with respect to the cell adhesion and proliferation, and these new biodegradable P(BS-co-CC) samples were found to exhibit as low cell toxicity as the PLLA control, particularly the two samples of poly(butylene succinate-co-18.7 mol % dimethyl

Amino-siloxane composition and methods of using the same

Science.gov (United States)

O'Brien, Michael Joseph; Farnum, Rachel Lizabeth; Perry, Robert James

2018-03-20

An amino-siloxane composition is presented. The amino-siloxane composition includes structure (I): ##STR00001## wherein R1 is independently at each occurrence a C1-C5 aliphatic radical; R2 is a C3-C.4 aliphatic radical; R3 is a C1-C5 aliphatic radical or R4, wherein R4 comprises structure (II): ##STR00002## and X is an electron donating group. Methods of reducing an amount of carbon dioxide in a process stream using the amino-siloxane composition are also presented.

Biodegradation of Di-(2-ethylhexyl) Phthalate by Rhodococcus ruber YC-YT1 in Contaminated Water and Soil

OpenAIRE

Ting Yang; Lei Ren; Yang Jia; Shuanghu Fan; Junhuan Wang; Jiayi Wang; Ruth Nahurira; Haisheng Wang; Yanchun Yan

2018-01-01

Di-(2-ethylehxyl) phthalate (DEHP) is one of the most broadly representative phthalic acid esters (PAEs) used as a plasticizer in polyvinyl chloride (PVC) production, and is considered to be an endocrine-disrupting chemical. DEHP and its monoester metabolites are responsible for adverse effects on human health. An efficient DEHP-degrading bacterial strain Rhodococcus ruber YC-YT1, with super salt tolerance (0–12% NaCl), is the first DEHP-degrader isolated from marine plastic debris found in c...

Formation and detoxification of reactive intermediates in the metabolism of chlorinated ethenes

NARCIS (Netherlands)

van Hylckama Vlieg, Johan E.T.; Janssen, DB

2001-01-01

Short-chain halogenated aliphatics, such as chlorinated ethenes, constitute a large group of priority pollutants. This paper gives an overview on the chemical and physical properties of chlorinated aliphatics that are critical in determining their toxicological characteristics and recalcitrance to

Method for the production of primary amines

NARCIS (Netherlands)

Baldenius, Kai-Uwe; Ditrich, Klaus; Breurer, Michael; Navickas, Vaidotas; Janssen, Dick; Crismaru, Ciprian; Bartsch, Sebastian

2014-01-01

The present invention relates to a novel enzymatically catalyzed method for the production of aliphatic primary amines, which method comprises the enzymatic oxidation of a primary aliphatic alcohol catalyzed by an alcohol dehydrogenase, amination of the resulting oxocompound catalyzed by a

A terahertz transmission imaging based approach for liquid alcohol wettability investigation

Science.gov (United States)

Huang, Hui; Zhao, Hongwei; Zhang, Bo; Su, Yunyun; Jiang, Weixiang; Cai, Bin; You, Guanjun; Ma, Yan

2018-03-01

By using terahertz time-domain spectroscopy (THz-TDS), the transmission spectral images of a series of aliphatic monohydric liquid alcohols were investigated in this work. The image gray value indicated the non-uniform distribution of the liquid. After noise reduction, the depth distribution was computed from the image content, which depended on the wettability of the container surface by the liquid. Then the volume of the liquid crept up to the container surface was compared quantitatively. Our result showed that the surface wettability of the PS container surface by the liquids increased with the alcohol alkyl chain increasing, which was verified by the contact angle of the liquid and the surface. The study indicated that the THz image might offer a potential technique for detecting the wettability of liquid directly without an additional contact angle experiment.

Correlations Between retention indices and molecular structure of aliphatic alcohols and of their benzoyl derivatives on phenyl substituted polysiloxane stationary phases; Cromatografia en fase gaseosa sobre metilfenilpolisiloxanos. Estructura molecular y parametros de retencion para alcoholes y sus derivados benzoilados

Energy Technology Data Exchange (ETDEWEB)

Pias, J B; Gasco, L

1976-07-01

The retention indices of aliphatic alcohols of carbon number up to C{sub g}, and of their benzoyl derivatives up to C{sub 7}, were determined in columns packed with Chromo sorb G (AW-DMCS-HP) coated previously with 5% methyl, and methyl phenyl polysiloxanes with increasing polarity (SE-30, 0V-3, 0V-7, 0V-11, 0V-17 and OV-25). Correlations between retention indices and chain length for 1-alcohols, 2-alcohols, 3-alcohols, 1 , on -3-alcohols, 2-methyl-1-alcohols and for their corresponding benzoyl derivatives were calculated at 100, 120 and 140 degree centigree. In alcohols, a -CH{sub 2}- group increases I approximately 100 units, and in their benzoyl derivatives from 80 to 100 units. Dispersion indices {delta}l , and positional and structural increments {delta}I, were evaluated for -OH and benzoyl groups in terms of phase polarity and chain length. Effects of chain length, chain branching and double bond location on retention parameters were also studied. (Author) 23 refs.

Synthesis of fatty monoester lubricant base oil catalyzed by Fe-Zn ...

Indian Academy of Sciences (India)

J. Chem. Sci. Vol. 126, No. 4, July 2014, pp. 997–1003. c Indian Academy of Sciences. Synthesis of fatty ... environmental pollution which the conventional min- eral oil-based ... fication of a fatty acid or transesterification of veg- etable oil with a ...

Linearly concatenated cyclobutane (ladderane) lipids form a dense bacterial membrane

NARCIS (Netherlands)

Sinninghe Damsté, J.S.; Strous, M.; Rijpstra, W.I.C.; Hopmans, E.C.; Geenevasen, J.A.J.; Duin, A.C.T. van; Niftrik, L.A.; Jetten, M.S.M.

2002-01-01

Lipid membranes are essential to the functioning of cells, enabling the existence of concentration gradients of ions and metabolites. Microbial membrane lipids can contain three-, five-, six- and even seven-membered aliphatic rings, but four-membered aliphatic cyclobutane rings have never been

Rational synthesis of AB-type N-substituted core-functionalized naphthalene diimides (cNDIs).

Science.gov (United States)

Berezin, Andrey A; Sciutto, Andrea; Demitri, Nicola; Bonifazi, Davide

2015-04-17

Acid-mediated transformation of tetraethyl 2,6-diethoxynaphthalene-1,4,5,8-tetracarboxylate selectively affords the core-substituted naphthalene-anhydride-ester (cNAE) in quantitative yield. This anhydride can be selectively converted into hetero-N-substituted core-functionalized naphthalene diimides (cNDIs) through sequential condensation reactions in the presence of the precursor amine with very high isolated yields over four steps. The approach can be applied to prepare a large variety of heterocyclic, aromatic, and aliphatic heterodiimides.

Molecular characterization of BrMYB28 and BrMYB29 paralogous transcription factors involved in the regulation of aliphatic glucosinolate profiles in Brassica rapa ssp. pekinensis.

Science.gov (United States)

Baskar, Venkidasamy; Park, Se Won

2015-07-01

Glucosinolates (GSL) are one of the major secondary metabolites of the Brassicaceae family. In the present study, we aim at characterizing the multiple paralogs of aliphatic GSL regulators, such as BrMYB28 and BrMYB29 genes in Brassica rapa ssp. pekinensis, by quantitative real-time PCR (qRT-PCR) analysis in different tissues and at various developmental stages. An overlapping gene expression pattern between the BrMYBs as well as their downstream genes (DSGs) was found at different developmental stages. Among the BrMYB28 and BrMYB29 paralogous genes, the BrMYB28.3 and BrMYB29.1 genes were dominantly expressed in most of the developmental stages, compared to the other paralogs of the BrMYB genes. Furthermore, the differential expression pattern of the BrMYBs was observed under various stress treatments. Interestingly, BrMYB28.2 showed the least expression in most developmental stages, while its expression was remarkably high in different stress conditions. More specifically, the BrMYB28.2, BrMYB28.3, and BrMYB29.1 genes were highly responsive to various abiotic and biotic stresses, further indicating their possible role in stress tolerance. Moreover, the in silico cis motif analysis in the upstream regulatory regions of BrMYBs showed the presence of various putative stress-specific motifs, which further indicated their responsiveness to biotic and abiotic stresses. These observations suggest that the dominantly expressed BrMYBs, both in different developmental stages and under various stress treatments (BrMYB28.3 and BrMYB29.1), may be potential candidate genes for altering the GSL level through genetic modification studies in B. rapa ssp. pekinensis. Copyright © 2015. Published by Elsevier SAS.

Characterization of the pigment fraction in sweet bell peppers (Capsicum annuum L.) harvested at green and overripe yellow and red stages by offline multidimensional convergence chromatography/liquid chromatography-mass spectrometry.

Science.gov (United States)

Bonaccorsi, Ivana; Cacciola, Francesco; Utczas, Margita; Inferrera, Veronica; Giuffrida, Daniele; Donato, Paola; Dugo, Paola; Mondello, Luigi

2016-09-01

Offline multidimensional supercritical fluid chromatography combined with reversed-phase liquid chromatography was employed for the carotenoid and chlorophyll characterization in different sweet bell peppers (Capsicum annuum L.) for the first time. The first dimension consisted of an Acquity HSS C18 SB (100 × 3 mm id, 1.8 μm particles) column operated with a supercritical mobile phase in an ultra-performance convergence chromatography system, whereas the second dimension was performed in reversed-phase mode with a C30 (250 × 4.6 mm id, 3.0 μm particles) stationary phase combined with photodiode array and mass spectrometry detection. This approach allowed the determination of 115 different compounds belonging to chlorophylls, free xanthophylls, free carotenes, xanthophyll monoesters, and xanthophyll diesters, and proved to be a significant improvement in the pigments determination compared to the conventional one-dimensional liquid chromatography approach so far applied to the carotenoid analysis in the studied species. Moreover, the present study also aimed to investigate and to compare the carotenoid stability and composition in overripe yellow and red bell peppers collected directly from the plant, thus also evaluating whether biochemical changes are linked to carotenoid degradation in the nonclimacteric investigated fruits, for the first time. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Epistasis × environment interactions among Arabidopsis thaliana glucosinolate genes impact complex traits and fitness in the field

DEFF Research Database (Denmark)

Kerwin, Rachel E.; Feusier, Julie; Muok, Alise

2017-01-01

(GSL) defense chemistry, leaf damage, and relative fitness using mutant lines of Arabidopsis thaliana varying at pairs of causal aliphatic GSL defense genes to test the impact of epistatic and epistasis × environment interactions on adaptive trait variation. We found that aliphatic GSL accumulation...

Amino-siloxane composition and methods of using the same

Science.gov (United States)

O'Brien, Michael Joseph; Farnum, Rachel Lizabeth; Perry, Robert James

2016-08-30

An amino-siloxane composition is presented. The amino-siloxane composition includes structure (I): ##STR00001## wherein R.sup.1 is independently at each occurrence a C.sub.1-C.sub.5 aliphatic radical; R.sup.2 is a C.sub.3-C.sub.4 aliphatic radical; R.sup.3 is a C.sub.1-C.sub.5 aliphatic radical or R.sup.4, wherein R.sup.4 comprises structure (II): ##STR00002## and X is an electron donating group. Methods of reducing an amount of carbon dioxide in a process stream using the amino-siloxane composition are also presented.

Engineering cell factories for producing building block chemicals for bio-polymer synthesis.

Science.gov (United States)

Tsuge, Yota; Kawaguchi, Hideo; Sasaki, Kengo; Kondo, Akihiko

2016-01-21

Synthetic polymers are widely used in daily life. Due to increasing environmental concerns related to global warming and the depletion of oil reserves, the development of microbial-based fermentation processes for the production of polymer building block chemicals from renewable resources is desirable to replace current petroleum-based methods. To this end, strains that efficiently produce the target chemicals at high yields and productivity are needed. Recent advances in metabolic engineering have enabled the biosynthesis of polymer compounds at high yield and productivities by governing the carbon flux towards the target chemicals. Using these methods, microbial strains have been engineered to produce monomer chemicals for replacing traditional petroleum-derived aliphatic polymers. These developments also raise the possibility of microbial production of aromatic chemicals for synthesizing high-performance polymers with desirable properties, such as ultraviolet absorbance, high thermal resistance, and mechanical strength. In the present review, we summarize recent progress in metabolic engineering approaches to optimize microbial strains for producing building blocks to synthesize aliphatic and high-performance aromatic polymers.

Chemical Characterization of Major and Minor Compounds of Nut Oils: Almond, Hazelnut, and Pecan Nut

Directory of Open Access Journals (Sweden)

Gabriel D. Fernandes

2017-01-01

Full Text Available The aim of this work was to characterize the major and minor compounds of laboratory-extracted and commercial oils from sweet almond, hazelnut, and pecan nut. Oils from sweet almond, hazelnut, and pecan nut were obtained by means of an expeller system, while the corresponding commercial oils were provided from Vital Âtman (BR. The contents of triacylglycerols, fatty acids, aliphatic and terpenic alcohols, desmethyl-, methyl-, and dimethylsterols, squalene, and tocopherols were determined. Oleic, palmitic, and linoleic acids were the main fatty acids. Desmethylsterols were the principal minor compounds with β-sitosterol being the most abundant component. Low amounts of aliphatic and terpenic alcohols were also found. The major tocopherol in hazelnut and sweet almond oils was α-tocopherol, whereas γ-tocopherol prevailed in pecan nut oil. Principal component analysis made it possible for us to differentiate among samples, as well as to distinguish between commercial and laboratory-extracted oils. Heatmap highlighted the main variables featuring each sample. Globally, these results have brought a new approach on nut oil characterization.

Influence of chemical and structural evolution of dissolved organic matter on electron transfer capacity during composting

International Nuclear Information System (INIS)

He, Xiao-Song; Xi, Bei-Dou; Cui, Dong-Yu; Liu, Yong; Tan, Wen-Bin; Pan, Hong-Wei; Li, Dan

2014-01-01

Highlights: • Electron transfer capability (ETC) of compost-derived DOM was investigated. • Composting treatment increased the ETC of DOM from municipal solid wastes. • The ETC increase related to humic matter, and molecule weight, and N and S content. - Abstract: Dissolved organic matter (DOM) can mediate electron transfer and change chemical speciation of heavy metals. In this study, the electron transfer capability (ETC) of compost-derived DOM was investigated through electrochemical approaches, and the factors influencing the ETC were studied using spectral and elemental analysis. The results showed that the electron accepting capacity (EAC) and electron donating capacity (EDC) of compost-derived DOM were 3.29–40.14 μmol e− (g C) −1 and 57.1– 346.07 μmol e− (g C) −1 , respectively. Composting treatment increased the fulvic- and humic-like substance content, oxygenated aliphatic carbon content, lignin-derived aromatic carbon content, molecule weight, and N and S content of DOM, but decreased the aliphatic carbon content and the C and H content. This conversion increased the EDC and EAC of the DOM during composting

A new way to produce hyperketonemia: use of ketone ester in a case of Alzheimer's disease.

Science.gov (United States)

Newport, Mary T; VanItallie, Theodore B; Kashiwaya, Yoshihiro; King, Michael Todd; Veech, Richard L

2015-01-01

Providing ketone bodies to the brain can bypass metabolic blocks to glucose utilization and improve function in energy-starved neurons. For this, plasma ketones must be elevated well above the ≤ 0.2 mM default concentrations normally prevalent. Limitations of dietary methods currently used to produce therapeutic hyperketonemia have stimulated the search for better approaches. Described herein is a new way to produce therapeutic hyperketonemia, entailing prolonged oral administration of a potent ketogenic agent--ketone monoester (KME)--to a patient with Alzheimer's disease dementia and a pretreatment Mini-Mental State Examination score of 12. The patient improved markedly in mood, affect, self-care, and cognitive and daily activity performance. The KME was well tolerated throughout the 20-month treatment period. Cognitive performance tracked plasma β-hydroxybutyrate concentrations, with noticeable improvements in conversation and interaction at the higher levels, compared with predose levels. KME-induced hyperketonemia is robust, convenient, and safe, and the ester can be taken as an oral supplement without changing the habitual diet. Published by Elsevier Inc.

Effect of sugar fatty acid esters on rumen fermentation in vitro

OpenAIRE

Wakita, M.; Hoshino, S.

1987-01-01

1.The effect of sugar fatty acid esters (SFEs; currently used as food additives for human consumption) on rumen volatile fatty acids (VFA) and gas production was studied with sheep rumen contents in vitro.2. Some SFEs having monoester contents of more than 70% increased the molar proportion of propionate in conjunction with reduction in the acetate: propionate ratio when the individual SFE was added to rumen contents in a final concentration of 4 g/l. Laurate sugar ester was the most potent p...

Production, characterization and fuel properties of alternative diesel fuel from pyrolysis of waste plastic grocery bags

Science.gov (United States)

Pyrolysis of HDPE waste grocery bags followed by distillation resulted in a liquid hydrocarbon mixture that consisted of saturated aliphatic paraffins (96.8%), aliphatic olefins (2.6%), and aromatics (0.6%) that corresponded to the boiling range of conventional petroleum diesel fuel (#1 diesel 182–2...

Shear bond strength of a self‑etched resin cement to an indirect ...

African Journals Online (AJOL)

2014-11-15

Nov 15, 2014 ... 3M ESPE, St. Paul, MN, USA Silane treated glass powder, substituted dimethacrylate 1‑benzyl‑5‑phenyl‑barbic‑acid, calcium salt, silane treated silica, sodium p‑toluenesulfinate, 1,12‑dodecane dimethycrylate calcium hydroxide methacrylated aliphatic amine methacrylated aliphatic amine titanium dioxide.

A Green Approach for Allylations of Aldehydes and Ketones: Combining Allylborate, Mechanochemistry and Lanthanide Catalyst

Directory of Open Access Journals (Sweden)

Viviane P. de Souza

2016-11-01

Full Text Available Secondary and tertiary alcohols synthesized via allylation of aldehydes and ketones are important compounds in bioactive natural products and industry, including pharmaceuticals. Development of a mechanochemical method using potassium allyltrifluoroborate salt and water, to successfully perform the allylation of aromatic and aliphatic carbonyl compounds is reported for the first time. By controlling the grinding parameters, the methodology can be selective, namely, very efficient for aldehydes and ineffective for ketones, but by employing lanthanide catalysts, the reactions with ketones can become practically quantitative. The catalyzed reactions can also be performed under mild aqueous stirring conditions. Considering the allylation agent and its by-products, aqueous media, energy efficiency and use of catalyst, the methodology meets most of the green chemistry principles.

Long-chain aliphatic wax esters isolated from the sponge Chalinula saudensis (Demospongia along the Jeddah coast of the Red Sea

Directory of Open Access Journals (Sweden)

Abdulmohsin Al-Sofyani

2011-03-01

Full Text Available The sponge Chalinula saudensis, which occurs along the Jeddah coast, has only recently been isolated and identified. In this study, the total crude organic matter of the sponge was extracted by solvents. The total crude extract was further separated by partitioning it with hexane and water, then with water and chloroform, and finally with water and t-butanol. The chloroform layer was subjected to separation by preparative layer chromatography on silica. One fraction contained four long-chain fatty acid esters, C28H56O2, C30H60O2, C32H62O2 and C36H70 O2. The second ester, C30H60O2, has been identified in the fire corals Millepora dichotoma and Millepora platyphylla. The others have not previously been reported from marine organisms; however similar long-chain esters with different long aliphatic chains and with different molecular weights have been identified from other marine organisms. These compounds are normally waxy and their presence in Chalinula saudensis plays a vital role in the biosynthetic pathways. They also act as insulators against seasonal variations.A esponja Chalinula saudensis ocorre ao longo da costa de Jeddah, Arabia Saudita, mas apenas recentemente foi isolada e identificada. No presente estudo a matéria orgânica total da esponja foi extraída por solventes e o extrato foi separado por partição sucessiva através do emprego de hexano e água, clorofórmio e água e finalmente t-butanol e água. A camada contendo clorofórmio foi então separada por cromatografia em sílica. Os resultados mostraram a presença de ésteres de quatro ácidos graxos de cadeira longa (C28H56O2, C30H60O2, C32H62O2 e C36H70O2, sendo que o segundo deles foi também identificado nos corais Millepora dichotoma e Millepora platyphylla. Não se tem evidência da presença dos demais compostos em outros organismos marinhos, embora haja relatos para ésteres semelhantes de cadeia longa, mas contendo diferentes cadeias alifáticas e diferentes pesos

Characterization of Whole Grain Pasta: Integrating Physical, Chemical, Molecular, and Instrumental Sensory Approaches.

Science.gov (United States)

Marti, Alessandra; Cattaneo, Stefano; Benedetti, Simona; Buratti, Susanna; Abbasi Parizad, Parisa; Masotti, Fabio; Iametti, Stefania; Pagani, Maria Ambrogina

2017-11-01

The consumption of whole-grain food-including pasta-has been increasing steadily. In the case of whole-grain pasta, given the many different producers, it seems important to have some objective parameters to define its overall quality. In this study, commercial whole-grain pasta samples representative of the Italian market have been characterized from both molecular and electronic-senses (electronic nose and electronic tongue) standpoint in order to provide a survey of the properties of different commercial samples. Only 1 pasta product showed very low levels of heat damage markers (furosine and pyrraline), suggesting that this sample underwent to low temperature dry treatment. In all samples, the furosine content was directly correlated to protein structural indices, since protein structure compactness increased with increasing levels of heat damage markers. Electronic senses were able to discriminate among pasta samples according to the intensity of heat treatment during the drying step. Pasta sample with low furosine content was discriminated by umami taste and by sensors responding to aliphatic and inorganic compounds. Data obtained with this multidisciplinary approach are meant to provide hints for identifying useful indices for pasta quality. As observed for semolina pasta, objective parameters based on heat-damage were best suited to define the overall quality of wholegrain pasta, almost independently of compositional differences among commercial samples. Drying treatments of different intensity also had an impact on instrumental sensory traits that may provide a reliable alternative to analytical determination of chemical markers of heat damage in all cases where there is a need for avoiding time-consuming procedures. © 2017 Institute of Food Technologists®.

Bacterial community changes during bioremediation of aliphatic hydrocarbon-contaminated soil.

Science.gov (United States)

Militon, Cécile; Boucher, Delphine; Vachelard, Cédric; Perchet, Geoffrey; Barra, Vincent; Troquet, Julien; Peyretaillade, Eric; Peyret, Pierre

2010-12-01

The microbial community response during the oxygen biostimulation process of aged oil-polluted soils is poorly documented and there is no reference for the long-term monitoring of the unsaturated zone. To assess the potential effect of air supply on hydrocarbon fate and microbial community structure, two treatments (0 and 0.056 mol h⁻¹ molar flow rate of oxygen) were performed in fixed bed reactors containing oil-polluted soil. Microbial activity was monitored continuously over 2 years throughout the oxygen biostimulation process. Microbial community structure before and after treatment for 12 and 24 months was determined using a dual rRNA/rRNA gene approach, allowing us to characterize bacteria that were presumably metabolically active and therefore responsible for the functionality of the community in this polluted soil. Clone library analysis revealed that the microbial community contained many rare phylotypes. These have never been observed in other studied ecosystems. The bacterial community shifted from Gammaproteobacteria to Actinobacteria during the treatment. Without aeration, the samples were dominated by a phylotype linked to the Streptomyces. Members belonging to eight dominant phylotypes were well adapted to the aeration process. Aeration stimulated an Actinobacteria phylotype that might be involved in restoring the ecosystem studied. Phylogenetic analyses suggested that this phylotype is a novel, deep-branching member of the Actinobacteria related to the well-studied genus Acidimicrobium. FEMS Microbiology Ecology © 2010 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. No claim to original French government works.

Esters with imidazo [1,5-c] quinazoline-3,5-dione ring spectral characterization and quantum-mechanical modeling.

Science.gov (United States)

Hęclik, K; Szyszkowska, A; Trzybiński, D; Woźniak, K; Klasek, A; Zarzyka, I

2017-04-01

1-phenyl-2H,6H-imidazo[1,5-c]quinazoline-3,5-dione reacts with ethyl bromoacetate under mild conditions to give 2-(ethoxycarbonylmethyl)-1-phenyl-6H-imidazo[1,5-c]quinazoline-3,5-dione (MEPIQ) and next 2,6-bis(ethoxycarbonylmethyl)-1-phenylimidazo[1,5-c]quinazoline-3,5-dione (BEPIQ). The products were isolated at high yield and identified on the basis of IR, 1 H- and 13 C-NMR, UV spectroscopy, and X-ray crystallography. Diester (BEPIQ) can be presented by 16 possible pair of enantiomers. Only one pair of them is the most stable and crystallizes which is shown crystallographic research. Based on quantum-mechanical modeling, with the use of DFT method, which conformers of mono- and diester and why they were formed was explained. It was calculated that 99.93% of the monoester (MEPIQ) is formed at position No. 2 and one pair of the monoester conformers, from six possible, has the largest share (51.63%). These results afforded to limit the number of diester conformers to eight. Unfortunately, the quantum-mechanical calculations performed that their shares are similar. Further quantum-mechanical modeling showed that conformers are able to undergo mutual transformations. As a result only one pair of diester conformers forms crystals. These conformers have substituents in trans position and these substituents are located parallel to imidazoquinazoline ring. This allows for the denser packing of the molecules in the unit cell.

Amino-siloxane composition and methods of using the same

Energy Technology Data Exchange (ETDEWEB)

O' Brien, Michael Joseph; Farnum, Rachel Lizabeth; Perry, Robert James

2018-03-20

An amino-siloxane composition is presented. The amino-siloxane composition includes structure (I): ##STR00001## wherein R¹ is independently at each occurrence a C₁-C₅ aliphatic radical; R² is a C₃-C.₄ aliphatic radical; R³ is a C₁-C₅ aliphatic radical or R⁴, wherein R⁴ comprises structure (II): ##STR00002## and X is an electron donating group. Methods of reducing an amount of carbon dioxide in a process stream using the amino-siloxane composition are also presented.

Reconstruction of anthropogenic activities on the excavations of a fireplace sequence from the Krems-Wachtberg site (Austria) using molecular proxies

Science.gov (United States)

Wiesenberg, Guido; Hambach, Ulrich

2010-05-01

The well investigated Krems-Wachtberg excavation yielded a broad variety of anthropogenic artefacts and thus enables a proper reconstruction of an ancient settlement of Upper-Palaeolithic age. Despite these artefacts, some questions cannot be answered by sedimentologic and archaeologic approaches. Molecular fossils like lipids including aliphatic hydrocarbons are suitable to improve understanding of e.g. paleoclimatic, pedogenetic, and archaeologic contexts. Especially aliphatic hydrocarbons including straight-chain and branched alkanes yield potential to elucidate biogenic sources of soil and loess organic matter and to assess degradation conditions of primary organic matter. To improve understanding on the terms the fireplaces at the Krems-Wachtberg site are used, aliphatic hydrocarbons are investigated on a set of samples covering several horizons in the context of one fireplace, which was part of the excavation. Horizons above and below the fireplace as well as the fireplace itself were investigated for lipids. Additionally, reference loess samples from a similar age like the fireplace and a pit filling were investigated. Two replicates were available for most samples except for the pit filling. Two distinct fireplace series have been studies. All samples were extracted for lipids using Soxhlet extraction followed by column chromatography in order to separate the aliphatic hydrocarbon fraction from other lipids. Thereafter, aliphatic hydrocarbons were quantified using gas chromatography. The total amounts of extractable organic compounds in the whole sample set from the Krems-Wachtberg site were in the range of usual loess deposits and accounted for 30-80 mg kg-1 loess. The largest contents were observed in reference loess samples and decreased within the excavation from fireplaces > sediments covering fireplace > basement of fireplace > pit. The lower the extract yields, the stronger was the degradation of organic matter. In this context, the pit yielded

Organic Nano-Grains in Comet 103P/Hartley 2: The Organic Glue of Porous Aggregate Grains?

Science.gov (United States)

Wooden, D. H.; Russo, N.Dello; Li, A.; Woodward, C. E.; Kelley, M. S.; Harker, D. E.; Cook, J. C.; Vervack, R. J.; Geballe, T. R.

2013-01-01

The GNIRS instrument on the Gemini 8-­-m telescope observed comet 103P/Hartley on 2010-­- Dec-­-04UT, a month after the EPOXI Mission encounter, and detected the 3.3 and 3.4 um bands in emission. The 3.3/3.4 ratio and the broad band widths are consistent with experiments of heated (approximately 600 K) aliphatic carbon (-CH3, -CH2) thin films. For the 3.4 micron band to be in emission, the aliphatic bonds must be attached to a carrier possessing the strongly UV-­-absorbing C=C aromatic rings, and these rings have to be less than 50-­-100 carbon atoms (4-6 Angstrom) for attached -CH bonds to also generate a 3.3 micron-band in emission. Slightly larger (=10Å) Very Small Grains (VSGs) can absorb single UV photons comparable to or exceeding their heat capacity, thermally fluctuate and release IR photon(s). The 3.3 micron and 3.4 micron bands observed by GNIRS suggest that organic macromolecules/ nano-­-grains with both aliphatic and aromatic bonds are fluorescing/thermally fluctuating in the coma. Aliphatic and aromatic materials have been seen in Stardust samples and the primitive carbonaceous chondrite 'Tagish Lake'. The larger the ratio of the -CH2/-CH3 components of the aliphatic 3.4 micron band, the more 'primitive' the organic material. In a Stardust organic globule, some aliphatic bonds were transformed into aromatic bonds during the low dosage of Transmission Electron Microscope imaging. Conversely, lab experiments show irradiation of ices containing small PAHs generates aliphatic organics. Photo-­-processing of ices also likely forms the ubiquitous aliphatic coatings that appear on the surfaces of all silicate subgrains constituting nine cometary interplanetary dust particles. The aliphatic coatings, dominated by -CH2, likely were important in sticking the aggregates together, and existed prior to incorporation of dust aggregates into comet nuclei. These comet aliphatics may be some of the sought-­-after precursors to the more robust and complex

Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines.

Science.gov (United States)

Ikawa, Takashi; Fujita, Yuki; Mizusaki, Tomoteru; Betsuin, Sae; Takamatsu, Haruki; Maegawa, Tomohiro; Monguchi, Yasunari; Sajiki, Hironao

2012-01-14

Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH(4)OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.

Enzymatic synthesis of sorbitan esters using a low-boiling-point azeotrope as a reaction solvent.

Science.gov (United States)

Sarney, D B; Barnard, M J; Virto, M; Vulfson, E N

1997-05-20

Sorbitan esters were prepared by controlled dehydration of sorbitol followed by lipase-catalyzed esterification of the resulting "sorbitan." The reaction was carried out in azeotropic mixtures of tert-butanol/n-hexane. A partial phase diagram to determine the temperature required for the distillation of the azeotrope at a given ratio of the solvents was constructed. The effect of varying concentrations of the two solvents on the rate of esterification and the monoester/diester ratio of the final product was investigated in detail. (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 54: 351-356, 1997.

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

Science.gov (United States)

2015-01-01

Monoselective γ-C–H olefination and carbonylation of aliphatic acids has been accomplished by using a combination of a quinoline-based ligand and a weakly coordinating amide directing group. The reaction provides a new route for constructing richly functionalized all-carbon quaternary carbon centers at the β-position of aliphatic acids. PMID:24666182

21 CFR 176.170 - Components of paper and paperboard in contact with aqueous and fatty foods.

Science.gov (United States)

2010-04-01

... suitable method) and using a test sample prepared by dissolving 5 grams of moisture-free hydroxypropyl guar... aliphatic diamines and/or their self-condensation products, and/or (ii) prepolymers produced by reacting 1,2... comprising at least 95 percent by weight C4 to C6 aliphatic diamines and/or their seIf-condensation products...

Identification of genotoxic compounds in crude oil using fractionation according to distillation, polarity and Kow.

Science.gov (United States)

Park, Shin Yeong; Lee, Hyo Jin; Khim, Jong Seong; Kim, Gi Beum

2017-01-30

We examined the degree of DNA damage caused by fractions of crude oil in accordance with the boiling points, polarity and log K ow . Relatively high DNA damage was observed in the aromatic fraction (290-330°C) and resin and polar fraction (350-400°C). The resin and polar fraction showed relatively high genotoxicity compared with the aliphatic and aromatic fraction at the 1-4 log K ow range. At the 6-7 log K ow range, the aromatic fraction showed relatively high DNA damage compared with the aliphatic and resin and polar fraction. In particular, every detailed fraction in accordance with the log K ow values (aliphatic and aromatic (310-320°C) and resins and polar fractions (370-380°C)) showed one or less than one DNA damage. However, the fractions before separation in accordance with log K ow values (aliphatic and aromatic (310-320°C) and resin and polar (370-380°C) fractions) showed high DNA damage. Thus, we confirm the synergistic action between the detailed compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

Acid extraction by supported liquid membranes containing basic carriers

International Nuclear Information System (INIS)

Danesi, P.R.; Cianetti, C.; Horwitz, E.P.

1983-01-01

The extraction of HNO 3 (nitric acid) from aqueous solutions by permeation through a number of supported liquid membranes containing basic carriers dissolved in diethylbenzene has been studied. The results have shown that the best permeations are obtained with long chain aliphatic amines (TLA, Primene JM-T) followed by TOPO (trioctylphosphine oxide) and then by other monofunctional and bifunctional organophosphorous basic carriers. The influence of an aliphatic diluent on the permeability of HNO 3 through a supported liquid membrane containing TLA as carrier was also investigated. In this case the permeability to HNO 3 decreases as a result of the lower diffusion coefficient of the acid-carrier complex in the more vicous aliphatic solvent. 4 figures

Conformational kinetics of aliphatic tails

Science.gov (United States)

Ferrarini, Alberta; Moro, Giorgio; Nordio, Pier Luigi

The master equation describing the random walk between sites identified with the stable conformers of a chain molecule, represents the extension to the time domain of the Rotational Isomeric State model. The asymptotic analysis of the multidimensional diffusion equation in the continuous torsional variables subjected to the configurational potential, provides a rigorous justification for the discrete models, and it supplies, without resorting to phenomenological parameters, molecular definitions of the kinetic rates for the conformational transitions occurring at each segment of the chain. The coupling between the torsional variables is fully taken into account, giving rise to cooperative effects. A complete calculation of the specific correlation functions which describe the time evolution of the angular functions probed by N.M.R. and dielectric relaxation measurements, has been performed for alkyl chains attached to a massive core. The resulting behaviour has been compared with the decay of trans and gauche populations of specific bonds, expressed in terms of suitable correlation functions whose time integrals lead quite naturally to the definition of effective kinetic constants for the conformational transitions.

ANTHOCYANINS ALIPHATIC ALCOHOLS EXTRACTION FEATURES

Directory of Open Access Journals (Sweden)

P. N. Savvin

2015-01-01

Full Text Available Anthocyanins red pigments that give color a wide range of fruits, berries and flowers. In the food industry it is widely known as a dye a food additive E163. To extract from natural vegetable raw materials traditionally used ethanol or acidified water, but in same technologies it’s unacceptable. In order to expand the use of anthocyanins as colorants and antioxidants were explored extracting pigments alcohols with different structures of the carbon skeleton, and the position and number of hydroxyl groups. For the isolation anthocyanins raw materials were extracted sequentially twice with t = 60 C for 1.5 hours. The evaluation was performed using extracts of classical spectrophotometric methods and modern express chromaticity. Color black currant extracts depends on the length of the carbon skeleton and position of the hydroxyl group, with the alcohols of normal structure have higher alcohols compared to the isomeric structure of the optical density and index of the red color component. This is due to the different ability to form hydrogen bonds when allocating anthocyanins and other intermolecular interactions. During storage blackcurrant extracts are significant structural changes recoverable pigments, which leads to a significant change in color. In this variation, the stronger the higher the length of the carbon skeleton and branched molecules extractant. Extraction polyols (ethyleneglycol, glycerol are less effective than the corresponding monohydric alcohols. However these extracts saved significantly higher because of their reducing ability at interacting with polyphenolic compounds.

Thermal Properties of Aliphatic Polypeptoids

KAUST Repository

Fetsch, Corinna; Luxenhofer, Robert

2013-01-01

A series of polypeptoid homopolymers bearing short (C1-C5) side chains of degrees of polymerization of 10-100 are studied with respect to thermal stability, glass transition and melting points. Thermogravimetric analysis of polypeptoids suggests

Thermal Properties of Aliphatic Polypeptoids

KAUST Repository

Fetsch, Corinna

2013-01-29

A series of polypeptoid homopolymers bearing short (C1-C5) side chains of degrees of polymerization of 10-100 are studied with respect to thermal stability, glass transition and melting points. Thermogravimetric analysis of polypeptoids suggests stability to >200 °C. The study of the glass transition temperatures by differential scanning calorimetry revealed two dependencies. On the one hand an extension of the side chain by constant degree of polymerization decrease the glass transition temperatures (Tg) and on the other hand a raise of the degree of polymerization by constant side chain length leads to an increase of the Tg to a constant value. Melting points were observed for polypeptoids with a side chain comprising not less than three methyl carbon atoms. X-ray diffraction of polysarcosine and poly(N-ethylglycine) corroborates the observed lack of melting points and thus, their amorphous nature. Diffractograms of the other investigated polypeptoids imply that crystalline domains exist in the polymer powder. © 2013 by the authors.

Aliphatic amine oxides as ligands

International Nuclear Information System (INIS)

Garla, L.C.; Betarello, V.H.; Chiericato Junior, G.; De Giovani, W.F.

1984-01-01

The reaction between some hydrated lanthanide perchlorates with trimethylamine oxide (TMAO) was studied. Compounds of general formula Ln(Cl 4 ) 3 : . 5,5 TMAO (Ln = La, Pr, Er and Y) were isolated. (Author) [pt

Adhesive compositions and methods

Science.gov (United States)

Allen, Scott D.; Sendijarevic, Vahid; O'Connor, James

2017-12-05

The present invention encompasses polyurethane adhesive compositions comprising aliphatic polycarbonate chains. In one aspect, the present invention encompasses polyurethane adhesives derived from aliphatic polycarbonate polyols and polyisocyanates wherein the polyol chains contain a primary repeating unit having a structure:. In another aspect, the invention provides articles comprising the inventive polyurethane compositions as well as methods of making such compositions.

Influence of chemical and structural evolution of dissolved organic matter on electron transfer capacity during composting

Energy Technology Data Exchange (ETDEWEB)

He, Xiao-Song [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Innovation base of Ground Water and Environmental System Engineering, Chinese Research Academy of Environmental Science, Beijing 100012 (China); Xi, Bei-Dou, E-mail: hexs82@126.com [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Innovation base of Ground Water and Environmental System Engineering, Chinese Research Academy of Environmental Science, Beijing 100012 (China); Cui, Dong-Yu [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Innovation base of Ground Water and Environmental System Engineering, Chinese Research Academy of Environmental Science, Beijing 100012 (China); Liu, Yong [Guangdong Key Laboratory of Agro-Environmental Integrated Control, Guangdong Institute of Eco-Environmental and Soil Sciences, Guangzhou 510650 (China); Tan, Wen-Bin; Pan, Hong-Wei; Li, Dan [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Innovation base of Ground Water and Environmental System Engineering, Chinese Research Academy of Environmental Science, Beijing 100012 (China)

2014-03-01

Highlights: • Electron transfer capability (ETC) of compost-derived DOM was investigated. • Composting treatment increased the ETC of DOM from municipal solid wastes. • The ETC increase related to humic matter, and molecule weight, and N and S content. - Abstract: Dissolved organic matter (DOM) can mediate electron transfer and change chemical speciation of heavy metals. In this study, the electron transfer capability (ETC) of compost-derived DOM was investigated through electrochemical approaches, and the factors influencing the ETC were studied using spectral and elemental analysis. The results showed that the electron accepting capacity (EAC) and electron donating capacity (EDC) of compost-derived DOM were 3.29–40.14 μmol{sub e−} (g C){sup −1} and 57.1– 346.07 μmol{sub e−} (g C){sup −1}, respectively. Composting treatment increased the fulvic- and humic-like substance content, oxygenated aliphatic carbon content, lignin-derived aromatic carbon content, molecule weight, and N and S content of DOM, but decreased the aliphatic carbon content and the C and H content. This conversion increased the EDC and EAC of the DOM during composting.

Biodegradable magnesium alloys for orthopaedic applications: A review on corrosion, biocompatibility and surface modifications.

Science.gov (United States)

Agarwal, Sankalp; Curtin, James; Duffy, Brendan; Jaiswal, Swarna

2016-11-01

Magnesium (Mg) and its alloys have been extensively explored as potential biodegradable implant materials for orthopaedic applications (e.g. Fracture fixation). However, the rapid corrosion of Mg based alloys in physiological conditions has delayed their introduction for therapeutic applications to date. The present review focuses on corrosion, biocompatibility and surface modifications of biodegradable Mg alloys for orthopaedic applications. Initially, the corrosion behaviour of Mg alloys and the effect of alloying elements on corrosion and biocompatibility is discussed. Furthermore, the influence of polymeric deposit coatings, namely sol-gel, synthetic aliphatic polyesters and natural polymers on corrosion and biological performance of Mg and its alloy for orthopaedic applications are presented. It was found that inclusion of alloying elements such as Al, Mn, Ca, Zn and rare earth elements provides improved corrosion resistance to Mg alloys. It has been also observed that sol-gel and synthetic aliphatic polyesters based coatings exhibit improved corrosion resistance as compared to natural polymers, which has higher biocompatibility due to their biomimetic nature. It is concluded that, surface modification is a promising approach to improve the performance of Mg-based biomaterials for orthopaedic applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of Polystyrene-Based Random Copolymers with Balanced Number of Basic or Acidic Functional Groups

DEFF Research Database (Denmark)

Dimitrov, Ivaylo; Jankova Atanasova, Katja; Hvilsted, Søren

2010-01-01

for the functionalization were applied. The first one involved direct functionalization of the template backbone through alkylation of the phenolic groups with suitable reagents. The second modification approach was based on "click" chemistry, where the introduction of alkyne groups onto the template backbone was followed......Pairs of polystyrene-based random copolymers with balanced number of pendant basic or acidic groups were synthesized utilizing the template strategy. The same poly[(4-hydroxystyrene)-ran-styrene] was used as a template backbone for modification. Two different synthetic approaches...... by copper-catalyzed 1,3 cycloaddition of aliphatic sulfonate- or amine-contaning azides. Both synthetic approaches proved to be highly efficient as evidenced by H-1-NMR analyses. The thermal properties were evaluated by differential scanning calorimetry and thermal gravimetric analyses and were influenced...

Manure biochar influence upon soil properties, phosphorus distribution and phosphatase activities: A microcosm incubation study.

Science.gov (United States)

Jin, Yi; Liang, Xinqiang; He, Miaomiao; Liu, Yu; Tian, Guangming; Shi, Jiyan

2016-01-01

Using manure-derived-biochar as an alternative phosphorus (P) source has bright future prospects to improve soil P status. A 98-day microcosm incubation experiment was set up for two soils which were amended with manure biochar at proportions of 0, 0.5% and 1.5%. Swine manure samples were air-dried and manure biochar was prepared by pyrolysis at 400 °C for 4 h. As determined by P-31 nuclear magnetic resonance ((31)P NMR) spectroscopy, manure biochar mainly increased the contents and fractions of orthophosphate and pyrophosphate in two soils, while decreased those of monoesters (P<0.05). At the end of incubation, 1.5% of manure biochar raised soil pH by 0.5 and 0.6 units, cation exchange capacity by 16.9% and 32.2%, and soil total P by 82.1% and 81.1% for silt loam and clay loam soils, respectively, as compared with those soils without biochar. Simultaneously, 1.5% of manure biochar decreased acid phosphomonoesterase activities by 18.6% and 34.0% for clay loam and silt loam, respectively; while it increased alkaline phosphomonoesterase activities by 28.5% and 95.1% for clay loam and silt loam, respectively. The enhancement of soil P availability after manure biochar addition was firstly due to the orthophosphate and pyrophosphate as the major P species in manure biochar which directly increased contents of soil inorganic P, and also attributed to the decomposition of some organic P like monoesters by enhanced alkaline phosphomonoesterase activities from manure biochar addition. Copyright © 2015 Elsevier Ltd. All rights reserved.